阅读说明：本技术 聚硅氧烷-聚亚烷基二醇嵌段共聚物及其制造方法 (Polysiloxane-polyalkylene glycol block copolymer and method for producing same ) 是由 井砂友香 宫浦健志 浅野到 于 2019-08-06 设计创作，主要内容包括：一种聚硅氧烷-聚亚烷基二醇嵌段共聚物,是通过使具有选自羧酸酐基、羟基、环氧基、氨基、和硫醇基中的官能团的聚硅氧烷(A)与具有选自羧酸酐基、羟基、氨基、环氧基、和硫醇基中的官能团的聚亚烷基二醇(B)反应而获得聚硅氧烷-聚亚烷基二醇嵌段共聚物中间体,进一步使该聚硅氧烷-聚亚烷基二醇嵌段共聚物中间体的羧基的一部分与对羧基具有反应性的化合物进行反应而获得的聚硅氧烷-聚亚烷基二醇嵌段共聚物,将该聚硅氧烷-聚亚烷基二醇嵌段共聚物整体设为100质量％,来源于聚硅氧烷(A)的结构的含量为30质量％以上且70质量％以下,并且,该聚硅氧烷-聚亚烷基二醇嵌段共聚物的羧基含量为0.1mmol/g～0.75mmol/g,重均分子量为5,000～500,000。提供在配合于环氧树脂的情况下,在环氧树脂中分散良好,能够进行环氧树脂固化物的低应力化的聚硅氧烷-聚亚烷基二醇嵌段共聚物。(A polysiloxane-polyalkylene glycol block copolymer obtained by reacting a polysiloxane (A) having a functional group selected from a carboxylic acid anhydride group, a hydroxyl group, an epoxy group, an amino group and a thiol group with a polyalkylene glycol (B) having a functional group selected from a carboxylic acid anhydride group, a hydroxyl group, an amino group, an epoxy group and a thiol group to obtain a polysiloxane-polyalkylene glycol block copolymer intermediate, and further reacting a part of the carboxyl group of the polysiloxane-polyalkylene glycol block copolymer intermediate with a compound reactive with the carboxyl group, wherein the polysiloxane-polyalkylene glycol block copolymer is 100% by mass as a whole and the content of a structure derived from the polysiloxane (A) is 30 to 70% by mass, the polysiloxane-polyalkylene glycol block copolymer has a carboxyl group content of 0.1 to 0.75mmol/g and a weight average molecular weight of 5,000 to 500,000. Provided is a polysiloxane-polyalkylene glycol block copolymer which, when blended with an epoxy resin, disperses well in the epoxy resin and enables the cured epoxy resin to be reduced in stress.)

1. A polysiloxane-polyalkylene glycol block copolymer obtained by reacting a polysiloxane (A) having a functional group selected from the group consisting of a carboxylic acid anhydride group, a hydroxyl group, an epoxy group, an amino group and a thiol group with a polyalkylene glycol (B) having a functional group selected from the group consisting of a carboxylic acid anhydride group, a hydroxyl group, an amino group, an epoxy group and a thiol group to obtain a polysiloxane-polyalkylene glycol block copolymer intermediate, and further reacting a part of the carboxyl group of the polysiloxane-polyalkylene glycol block copolymer intermediate with a compound reactive with the carboxyl group, wherein the polysiloxane-polyalkylene glycol block copolymer is 100% by mass as a whole and the content of a structure derived from the polysiloxane (A) is 30 to 70% by mass, the polysiloxane-polyalkylene glycol block copolymer has a carboxyl group content of 0.1 to 0.75mmol/g and a weight average molecular weight of 5,000 to 500,000.

2. The polysiloxane-polyalkylene glycol block copolymer of claim 1, wherein the compound reactive with carboxyl groups is selected from orthoesters,At least 1 compound selected from the group consisting of oxazolines, epoxies, alcohols, monophenols, haloalkanes, and alkyl carbonates.

3. The polysiloxane-polyalkylene glycol block copolymer according to claim 1 or 2, which has a product of the number average molecular weight and the carboxyl group content of more than 2.

4. The polysiloxane-polyalkylene glycol block copolymer according to any one of claims 1 to 3, wherein the polysiloxane (A) is represented by the general formula (1),

wherein X is a functional group selected from the group consisting of a carboxylic anhydride group, a hydroxyl group, an epoxy group, an amino group and a thiol group, and each of them may be the same or different; r¹Hydrogen atom, alkyl group having 1 to 5 carbon atoms or phenyl group, which may be the same or different; r²A single bond, a 2-valent aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms, or a 2-valent hydrocarbon ether group having 1 to 10 carbon atoms, each of which may be the same or different; n represents a number of repeating units of 5 to 100.

5. The polysiloxane-polyalkylene glycol block copolymer according to any one of claims 1 to 4, wherein the polyalkylene glycol (B) is represented by the general formula (2),

wherein Y is a functional group selected from the group consisting of a carboxylic anhydride group, a hydroxyl group, an amino group, an epoxy group and a thiol group, and each of them may be the same or different; r³The alkyl group is a straight chain or branched chain alkyl group with 2-10 carbon atoms, and the alkyl groups can be the same or different; m represents the number of repeating units of 3 to 300.

6. The polysiloxane-polyalkylene glycol block copolymer according to any one of claims 1 to 5, which comprises a structure derived from a copolymerization component (C) having 1 or more functional groups capable of reacting with the functional group of the polysiloxane (A) and/or the functional group of the polyalkylene glycol (B).

7. The polysiloxane-polyalkylene glycol block copolymer according to any one of claims 1 to 6, wherein the polyalkylene glycol (B) is poly (1, 4-butanediol) and/or polypropylene glycol.

8. A method for producing a polysiloxane-polyalkylene glycol block copolymer, wherein the following step (2) is performed after the following step (1);

step (1): a step of reacting a polysiloxane (a) having a functional group selected from a carboxylic acid anhydride group, a hydroxyl group, an epoxy group, an amino group and a thiol group with a polyalkylene glycol (B) having a functional group selected from a carboxylic acid anhydride group, a hydroxyl group, an amino group, an epoxy group and a thiol group to obtain a polysiloxane-polyalkylene glycol block copolymer intermediate;

step (2): is a step of reacting a carboxyl group of the intermediate polysiloxane-polyalkylene glycol block copolymer obtained in the step (1) with a compound having reactivity with a carboxyl group selected from orthoesters,At least 1 compound selected from the group consisting of oxazolines, epoxies, alcohols, monophenols, haloalkanes, and alkyl carbonates.

9. The method for producing a polysiloxane-polyalkylene glycol block copolymer according to claim 8, wherein in the step (1), the polysiloxane (a), the polyalkylene glycol (B), and a copolymerization component (C) capable of reacting with a functional group of the polysiloxane (a) and/or a functional group of the polyalkylene glycol (B) are reacted.

10. The method for producing a polysiloxane-polyalkylene glycol block copolymer according to claim 8 or 9, wherein in the step (1), a copolymerization component (C) is a copolymerization component (C') capable of reacting with both the functional group of the polysiloxane (a) and the functional group of the polyalkylene glycol (B).

11. The method for producing a polysiloxane-polyalkylene glycol block copolymer according to any one of claims 8 to 10, wherein the polysiloxane-polyalkylene glycol block copolymer is 100% by mass as a whole, the content of the structure derived from the polysiloxane (A) in the obtained polysiloxane-polyalkylene glycol block copolymer is 30% by mass or more and 70% by mass or less, and the carboxyl group content is 0.1 to 0.75 mmol/g.

12. The method for producing a polysiloxane-polyalkylene glycol block copolymer according to any one of claims 8 to 11, wherein in the step (1), the reaction is carried out without using a metal catalyst as a reaction accelerator.

13. An epoxy resin composition comprising the polysiloxane-polyalkylene glycol block copolymer according to any one of claims 1 to 7 and an epoxy resin.

14. An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 13.

Technical Field

The present invention relates to a polysiloxane-polyalkylene glycol block copolymer suitable for use in an epoxy resin cured product such as a semiconductor sealing agent, and a method for producing the same.

Background

In recent years, miniaturization of electronic devices has been progressing. With this, the semiconductor package is thinned, and therefore, there is a problem that cracks are likely to be generated with a smaller stress than in the conventional case. In addition, in the future, demand for power semiconductors is expected to increase. Since the power semiconductor generates a large amount of heat, the use environment is heated, and peeling occurs at the interface due to the difference in thermal expansion coefficient between the chip and the sealing material, and the package is likely to be damaged. Thus, the semiconductor sealing material is required to have further reduced stress.

Semiconductor sealing materials are generally composed of various additives such as epoxy resins, curing agents, fillers, low-stress agents, flame retardants, and the like. For the purpose of reducing the stress of the semiconductor sealing material, there is a method of reducing the elastic modulus of the cured epoxy resin, and a compound containing polysiloxane as a main component is generally added as a stress reducer. However, since polysiloxane has poor dispersibility in cured epoxy resins, a technique of preparing an ABA type triblock copolymer in which polyalkylene glycol chains are modified at both ends of polysiloxane is known (patent document 1). Further, as a technique for further improving dispersibility in an epoxy resin cured product, a method of imparting a glycidyl group and a carboxyl group to a terminal of a multiblock copolymer composed of polysiloxane and polyalkylene glycol is disclosed (patent document 2).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 10-182831

Patent document 2: japanese laid-open patent publication No. 4-359023

Disclosure of Invention

Problems to be solved by the invention

As the characteristics of the low-stress agent added to the semiconductor sealing material, in addition to the low elastic modulus of the semiconductor sealing material, further added values such as improvement of fluidity and good dispersion in the matrix resin are required.

On the other hand, ABA type triblock copolymers in which polyalkylene glycol chains are modified at both ends of polysiloxane, and copolymers comprising polysiloxane and polyalkylene glycol in which glycidyl groups and carboxyl groups are added to the ends have problems such as insufficient effect of improving dispersibility and coarse dispersion in cured epoxy resins.

The present invention addresses the problem of providing a polysiloxane-polyalkylene glycol block copolymer which has excellent dispersibility in an epoxy resin cured product and which achieves low stress in the resulting epoxy resin cured product.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have achieved the following invention. Namely, the present invention is as follows.

< 1 > A polysiloxane-polyalkylene glycol block copolymer which is obtained by reacting a polysiloxane (A) having a functional group selected from the group consisting of a carboxylic acid anhydride group, a hydroxyl group, an epoxy group, an amino group and a thiol group with a polyalkylene glycol (B) having a functional group selected from the group consisting of a carboxylic acid anhydride group, a hydroxyl group, an amino group, an epoxy group and a thiol group to obtain a polysiloxane-polyalkylene glycol block copolymer intermediate, and further reacting a part of the carboxyl group of the polysiloxane-polyalkylene glycol block copolymer intermediate with a compound reactive with the carboxyl group, wherein the polysiloxane-polyalkylene glycol block copolymer is 100% by mass as a whole and the content of a structure derived from the polysiloxane (A) is 30 to 70% by mass, the polysiloxane-polyalkylene glycol block copolymer has a carboxyl group content of 0.1 to 0.75mmol/g and a weight average molecular weight of 5,000 to 500,000.

< 2 > a method for producing a polysiloxane-polyalkylene glycol block copolymer, wherein the following step (2) is carried out after the following step (1);

step (1): a step of reacting a polysiloxane (a) having a functional group selected from a carboxylic acid anhydride group, a hydroxyl group, an epoxy group, an amino group, and a thiol group with a polyalkylene glycol (B) having a functional group selected from a carboxylic acid anhydride group, a hydroxyl group, an amino group, an epoxy group, and a thiol group to obtain a polysiloxane-polyalkylene glycol block copolymer intermediate;

step (2): is a step of reacting a carboxyl group of the intermediate polysiloxane-polyalkylene glycol block copolymer obtained in the step (1) with a compound having reactivity with a carboxyl group selected from orthoesters,At least 1 compound selected from the group consisting of oxazolines, epoxies, alcohols, monophenols, haloalkanes, and alkyl carbonates.

< 3 > an epoxy resin composition comprising the above polysiloxane-polyalkylene glycol block copolymer and an epoxy resin.

< 4 > an epoxy resin cured product obtained by curing the epoxy resin composition.

ADVANTAGEOUS EFFECTS OF INVENTION

The polysiloxane-polyalkylene glycol block copolymer of the present invention is a block copolymer having polysiloxane which is incompatible with an epoxy resin but has excellent flexibility and polyalkylene glycol which is compatible with an epoxy resin and has excellent flexibility, and has both flexibility and good dispersibility in a cured epoxy resin. When the polysiloxane-polyalkylene glycol block copolymer of the present invention is blended with an epoxy resin, the polysiloxane-polyalkylene glycol block copolymer can be dispersed well in an epoxy resin cured product, and the stress of the epoxy resin cured product can be reduced. In a preferred embodiment, the decrease in fluidity caused by the addition of the polysiloxane-polyalkylene glycol block copolymer to the epoxy resin is also suppressed. Thus, the resin composition is useful as various additives such as a surfactant and a resin modifier, and is particularly suitable as a low-stress agent for a semiconductor sealing material.

Drawings

FIG. 1 is a TEM photograph of a cross-section of the cured epoxy resin obtained in example 1.

FIG. 2 is a TEM image of a cross-section of the cured epoxy resin obtained in example 2.

Detailed Description

The polysiloxane-polyalkylene glycol block copolymer of the present invention is a polysiloxane-polyalkylene glycol block copolymer (hereinafter, may be simply referred to as a block copolymer) obtained by reacting a polysiloxane (a) having a functional group selected from a carboxylic acid anhydride group, a hydroxyl group, an epoxy group, an amino group, and a thiol group with a polyalkylene glycol (B) having a functional group selected from a carboxylic acid anhydride group, a hydroxyl group, an amino group, an epoxy group, and a thiol group to obtain a polysiloxane-polyalkylene glycol block copolymer intermediate (hereinafter, may be simply referred to as a block copolymer), and further reacting a part of the carboxyl group of the polysiloxane-polyalkylene glycol block copolymer intermediate with a compound reactive with the carboxyl group, the polysiloxane-polyalkylene glycol block copolymer being 100% by mass as a whole, the content of the structure derived from the polysiloxane (A) is 30 to 70 mass%, and the polysiloxane-polyalkylene glycol block copolymer has a carboxyl group content of 0.1 to 0.75mmol/g and a weight average molecular weight of 5,000 to 500,000.

Here, the polysiloxane (a) having a functional group (hereinafter, may be simply referred to as polysiloxane (a)) and the polyalkylene glycol (B) having a functional group (hereinafter, may be simply referred to as polyalkylene glycol (B)) may be reacted with each other, the polysiloxane (a) having a functional group and the polyalkylene glycol (B) having a functional group may be directly reacted with each other and bonded to each other, or the polysiloxane (a) having a functional group and the polyalkylene glycol (B) having a functional group may be bonded to each other via a copolymerization component (C) capable of reacting with both the component (a) and the component (B). By this reaction, a polysiloxane-polyalkylene glycol block copolymer intermediate can be obtained.

In addition, when the polysiloxane (a) having a functional group is bonded via the copolymerization component (C), a block copolymer intermediate can be obtained even when the polysiloxane (a) having a functional group and the polyalkylene glycol (B) having a functional group do not directly react with each other.

In the case where polysiloxane (a) having a functional group is directly reacted with polyalkylene glycol (B) having a functional group, in order to impart a carboxyl group to the resulting block copolymer intermediate, it is necessary that either one of the functional groups of polysiloxane (a) and polyalkylene glycol (B) is a carboxylic anhydride group and the other functional group is a hydroxyl group, an epoxy group, an amino group or a thiol group. From the viewpoint of the viscosity of the obtained block copolymer intermediate, it is more preferable that one of the functional groups of the polysiloxane (a) and the polyalkylene glycol (B) is a carboxylic anhydride group, and the other functional group is a hydroxyl group, an amino group, or a thiol group. From the viewpoint of the heat resistance of the obtained block copolymer, it is further preferable that one of the functional groups of the polysiloxane (a) and the polyalkylene glycol (B) is a carboxylic anhydride group, and the other functional group is a hydroxyl group or an amino group.

When the functional group of the polysiloxane (a) and the functional group of the polyalkylene glycol (B) are directly reacted and bonded, a bond selected from an ester bond, an amide bond and a thioester bond is formed by the reaction of the polysiloxane (a) with the functional group of the polyalkylene glycol (B). Among them, an ester bond or a thioester bond is preferable from the viewpoint of viscosity, and an ester bond is more preferable from the viewpoint of heat resistance. In addition, the bonding portion of the obtained block copolymer intermediate contains a carboxyl group generated by the reaction.

In addition, a plurality of polysiloxanes (a) having different functional groups and/or a plurality of polyalkylene glycols (B) having different functional groups may be reacted.

The polysiloxane-polyalkylene glycol block copolymer of the present invention can be controlled to a desired carboxyl group content by reacting a part of the carboxyl groups of the block copolymer intermediate obtained by the above-mentioned operation with a compound reactive to the carboxyl groups. By this reaction, the carboxyl group is blocked to generate a substituent including a carboxylic acid derivative.

Specific examples of the compound having reactivity with a carboxyl group include an esterifying agent, an amidating agent and the like. The esterifying agent is a compound which reacts with a carboxyl group to form an ester bond, and the amidating agent is a compound which reacts with a carboxyl group to form an amide bond.

Examples of the esterifying agent include orthoesters,Oxazolines, epoxies, alcohols, monophenols, dimethylformamide dialkyl acetals, haloalkanes, and alkyl carbonates.

Specific examples of orthoesters include trimethyl orthoformate, trimethyl orthoacetate, triethyl orthoformate, triethyl orthoacetate, tripropylorthoformate, tripropylorthoacetate, tributylorthoformate, and tributylorthoacetate.

AsExamples of oxazolines include 2-methyl-2-Oxazoline, 2-ethyl-2-Oxazoline, 2-phenyl-2-Oxazoline, 2-propyl-2-Oxazoline, 2-isopropyl-2-Oxazoline, 2,4-trimethyl-2-Oxazoline, and the like. In useWhen the oxazoline is used as an esterifying agent, a substituent group containing a carboxylic acid derivative formed after the reaction is an ester group and has an amide group. In addition to this, the present invention is,oxazolines are preferred because they do not produce by-products in the reaction with carboxyl groups.

The epoxy group is a compound having an epoxy group, and specific examples thereof include propylene oxide, isobutylene oxide, 1, 2-butylene oxide, 1, 2-cyclopentane oxide, 1, 2-hexane oxide, 1, 2-heptane oxide, 1, 2-octane oxide, 1, 2-decane oxide, 1, 2-dodecane oxide, 1, 2-tetradecane oxide, 1, 2-hexadecane oxide, 1, 2-octadecane oxide, glycidyl methyl ether, ethyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, glycidyl lauryl ether, 2-biphenyl glycidyl ether, 1, 2-cyclohexene oxide, 1-methyl-1, a monofunctional epoxy compound such as 2-epoxycyclohexane or 2, 3-epoxynorbornane, a dibasic epoxy compound such as 1, 5-hexadiene diepoxide, 1, 7-octadiene diepoxide or bisphenol A diglycidyl ether. When an epoxy is used as the esterifying agent, a substituent containing a carboxylic acid derivative generated after the reaction is an ester group and has a hydroxyl group. The monofunctional epoxy compound is more preferable in terms of not lowering the fluidity.

Examples of the alcohol are compounds having a hydroxyl group, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-dimethyl-1-propanol (t-butyl alcohol), 2-methyl-1-butanol, 3-methyl-1-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-hexanol, 3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1-hexanol, 1-butanol, 2-butanol, 1-butanol, 2-pentanol, 2-methyl-1-pentanol, 3-, Benzyl alcohol, and the like.

Examples of the monophenols include phenol, 3-methylphenol, 3-tert-butylphenol, 3, 5-dimethylphenol, 3,4, 5-trimethylphenol, dibutylhydroxytoluene, cresol, eugenol, guaiacol, thymol, methyl salicylate, and propofol.

Examples of the dimethylformamide dialkyl acetals include N, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, N-dimethylformamide dipropyl acetal, N-dimethylformamide dibutyl acetal, N-dimethylformamide di-tert-butyl acetal, N-dimethylformamide dipentyl acetal, N-dimethylformamide dihexyl acetal, and the like.

Examples of the haloalkane include methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, propyl bromide, propyl iodide, butyl bromide, and butyl iodide.

Examples of the alkyl carbonates include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, and the like.

The esterification agent is preferably selected from orthoesters,Oxazoline compounds, epoxy compounds, alcohols, monophenols, haloalkanes, and alkyl carbonates. More preferably selected from the group consisting of orthoesters, from the group consisting of,Oxazoline compounds, and alkyl carbonate compounds. Orthoesters are preferable in terms of good low elastic modulus quantification effect. Among the orthoesters, trimethyl orthoformate, trimethyl orthoacetate, triethyl orthoformate, triethyl orthoacetate, tripropylorthoformate and tripropylorthoacetate are preferable from the viewpoint of excellent dispersibility in the cured epoxy resin.The oxazoline is preferable because of its excellent dispersibility in a cured epoxy resin. In thatAmong the oxazolines, 2-methyl-2-Oxazoline, 2-ethyl-2-Oxazoline, 2-phenyl-2-An oxazoline. The use of dialkyl acetals of dimethylformamide is not preferable because the fluidity may be lowered.

Examples of the amidating agent include amines. Specific examples thereof include methylamine, ethylamine, propylamine, butylamine, isobutylamine, tert-pentylamine, isopentylamine, sec-butylamine, pentylamine, 3-aminopentane, neopentylamine, 2-methylbutylamine, hexylamine, heptylamine, 3-dimethyl-2-butylamine, octylamine, nonylamine, 1-aminodecane, aniline, o-toluidine, m-toluidine, p-toluidine, 4-ethylaniline, 4-isopropylaniline, 4-tert-butylaniline, 2, 3-dimethylaniline, 2, 5-dimethylaniline, 2, 6-dimethylaniline, 3, 4-dimethylaniline, 3, 5-dimethylaniline, 2,4, 6-trimethylaniline, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, 1-aminopyrene, and the like. However, since the amine may cause poor fluidity if unreacted materials remain, it is preferable to remove the unreacted materials by purification and drying after the reaction until the fluidity is not lowered.

Further, the compound having reactivity with the carboxyl group may be used in 1 kind, or 2 or more kinds may be used in combination.

When a by-product is generated by the reaction between a compound reactive with a carboxyl group and the carboxyl group, if the by-product remains when mixed with an epoxy resin, the flowability may be decreased by an unexpected side reaction, or air bubbles may be taken into a cured epoxy resin to decrease the mechanical strength. Therefore, it is preferable to remove the by-products by purification and drying to such an extent that the effects are not obtained. From the viewpoint of ease of removal by drying, the boiling point of the by-product is preferably 130 ℃ or lower, more preferably 100 ℃ or lower, and particularly preferably 80 ℃ or lower. The drying conditions vary depending on the boiling point of the by-product, but it is preferably 200 ℃ or lower, more preferably 180 ℃ or lower, and particularly preferably 150 ℃ or lower under reduced pressure.

The amount of the compound having reactivity with respect to carboxyl groups is not particularly limited as long as the carboxyl group content of the obtained polysiloxane-polyalkylene glycol block copolymer is within a desired range, but is preferably 0.1 to 3.0 equivalents, more preferably 0.2 to 2.0 equivalents, even more preferably 0.4 to 1.5 equivalents, and particularly preferably 0.7 to 1.0 equivalents, relative to the carboxyl group content contained in the block copolymer intermediate before the reaction of the compound. The carboxyl group content can be determined by a known titration method as described later. For example, the block copolymer is dissolved in toluene or tetrahydrofuran, and the resulting solution is titrated with 0.1mol/L alcoholic potassium hydroxide using phenolphthalein as an indicator, and the value is calculated from the obtained value.

As the polysiloxane (A) having a functional group, a polysiloxane represented by the general formula (1) can be used.

In addition, n represents the number of repeating units of 5 to 100. X is a functional group selected from the group consisting of a carboxylic anhydride group, a hydroxyl group, an epoxy group, an amino group, and a thiol group. The carboxylic anhydride group here also includes cyclic carboxylic anhydride groups such as maleic anhydride, phthalic anhydride, and succinic anhydride. Furthermore, R¹Is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group. R²Is a group selected from a single bond, a 2-valent aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and a 2-valent hydrocarbon ether group having 1 to 10 carbon atoms. Here, the single bond means R²Absent and silicon is directly bonded to X. In addition, the slave ringFrom the viewpoint of improving dispersibility in an epoxy resin cured product, R²Preferably butylene, propylene or ethylene, most preferably propylene or ethylene. Further, when X is a cyclic carboxylic acid anhydride group, X and R²Or the bonding position with the silicon atom may be any position. The 2-valent hydrocarbon ether group is preferably represented by- (CH)₂)_a-O-(CH₂)_b-represents, and 1. ltoreq. a + b. ltoreq.10. All of R¹And R²And X may be the same or different.

R in the general formula (1)¹Is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, and is preferably a group which does not react with X, Y and the copolymerization component (C). If R is¹It is not preferable to react with X, Y or the copolymerization component (C) because it inhibits the reaction between X and Y or the progress of the crosslinking reaction. In addition, in R¹When the chain length of (b) is too long, the polysiloxane-alkylene glycol block copolymer obtained is undesirably increased in viscosity and reduced in molding processability when added to an epoxy resin. R¹Preferably any of propyl, ethyl and methyl, more preferably ethyl or methyl, most preferably methyl. Further, all R¹May be different or the same.

The polysiloxane (a) having a functional group is preferably a polyorganosiloxane having a functional group, and particularly preferably a polydimethylsiloxane having a functional group.

The weight average molecular weight of the polysiloxane (a) having a functional group is not particularly limited, and the lower limit thereof is preferably 500 or more, more preferably 800 or more, and further preferably 1,000 or more. The upper limit of the weight average molecular weight is preferably 8,000 or less, more preferably 5,000 or less, still more preferably 4,000 or less, and most preferably 3,000 or less. When the polysiloxane (a) having a functional group has a small weight average molecular weight, the effect of reducing the elastic modulus is low even when the polysiloxane-polyalkylene glycol block copolymer obtained is added to an epoxy resin. In addition, when the polysiloxane (a) having a functional group has a high weight average molecular weight, the polysiloxane (a) having a functional group and the polyalkylene glycol (B) having a functional group are separated and the reaction does not proceed in a uniform state, and thus the reactivity with the polyalkylene glycol (B) having a functional group is deteriorated. The weight average molecular weight of the polysiloxane (a) having a functional group is a weight average molecular weight in terms of polymethyl methacrylate, measured by gel permeation chromatography using Tetrahydrofuran (THF) as a solvent.

Examples of the polysiloxane having a functional group (A) include those commercially available from shin-Etsu chemical Co., Ltd, X-22-168AS, KF-105, X-22-163A, X-22-163B, X-22-163C, KF-8010, X-22-161A, X-161B, KF-8012, X-22-169AS, X-22-169B, X-22-160AS, KF-6001, KF-6002, KF-6003, X-22-1821, X-22-167B, X-22-167C, X-22-163, KF-6000, PAM-E, KF-8008, X-22-168A, X-22-168B, X-22-168-P5-B, X-22-1660B-3, X-22-9409, commercially available from Bay レ & ダウコーニング, BY16-871, BY16-853U, BY16-855, BY16-201, and the like.

Further, as the polyalkylene glycol (B) having a functional group, a polyalkylene glycol represented by the general formula (2) is preferably used.

In addition, m represents the number of repeating units of 3 to 300. Y is a functional group selected from the group consisting of a carboxylic anhydride group, a hydroxyl group, an amino group, an epoxy group, and a thiol group. The carboxylic anhydride group here also includes cyclic carboxylic anhydride groups such as maleic anhydride, phthalic anhydride, and succinic anhydride. R³Is a linear or branched alkyl group having 2 to 10 carbon atoms. At R³When the number of carbon atoms of (2) is more than 10, the polyalkylene glycol (B) having a functional group is not compatible with the epoxy resin, and the dispersibility of the resulting polysiloxane-polyalkylene glycol block copolymer in a cured epoxy resin is deteriorated, which is not preferable. In addition, R³When the number of carbon atoms of (2) is less than 2, flexibility is lowered, which is not preferable. R³The preferred number of carbon atoms of (3) or (4). All of R³And Y may be the same or different.

In the case where the functional group of the polysiloxane (a) is a carboxylic anhydride group, the poly-1, 4-butanediol and/or polypropylene glycol as the polyalkylene glycol (B) having a functional group is excellent in reactivity with the polysiloxane (a), the reaction proceeds without using a metal catalyst as a reaction accelerator, and the polysiloxane (a) reacts with the polyalkylene glycol (B) even without using an organic solvent, and a homogeneous block copolymer intermediate can be obtained, which is preferable. In particular, poly-1, 4-butanediol is more preferable from the viewpoint of improvement of heat resistance.

The weight average molecular weight of the polyalkylene glycol (B) having a functional group is not particularly limited, and the lower limit thereof is preferably 300 or more, more preferably 500 or more, and further preferably 1,000 or more. The upper limit of the weight average molecular weight is preferably 20,000 or less, more preferably 10,000 or less, still more preferably 5,000 or less, and most preferably 3,000 or less. When the weight average molecular weight of the functional group-containing polyalkylene glycol (B) is small, the polysiloxane-polyalkylene glycol block copolymer obtained has a poor effect of reducing the modulus of elasticity when added to an epoxy resin. In addition, when the weight average molecular weight of the polyalkylene glycol (B) having a functional group is large, the polysiloxane (a) having a functional group is phase-separated from the polyalkylene glycol (B) having a functional group, and the reaction in a uniform state does not proceed, so that the reactivity with the polysiloxane (a) having a functional group is deteriorated. The weight average molecular weight of the functional group-containing polyalkylene glycol (B) is a weight average molecular weight calculated as polymethyl methacrylate, measured by gel permeation chromatography using Tetrahydrofuran (THF) as a solvent.

The polysiloxane-alkylene glycol block copolymer obtained may be reacted with a copolymerization component (C) capable of reacting with the polysiloxane (A) and the polyalkylene glycol (B) in addition to the polysiloxane (A) and the polyalkylene glycol (B) within a range not impairing flexibility and good dispersibility in an epoxy resin.

The copolymerization component (C) is a compound having 1 or more functional groups capable of reacting with the functional group of the polysiloxane (A) and/or the functional group of the polyalkylene glycol (B). In this case, the obtained block copolymer has a structure derived from the copolymerization component (C) in addition to the structure derived from the polysiloxane (a) and the structure derived from the polyalkylene glycol (B).

This copolymerization component (C) is preferably dissolved in both the polysiloxane (a) and the polyalkylene glycol (B) during the reaction, because the reaction is easy to proceed. In addition, a plurality of copolymerization components (C) may be used.

Examples of the copolymerizable component (C) include monocarboxylic acid anhydride, dicarboxylic acid anhydride, diol, alcohol, monohydric phenol, dihydric phenol, diamine, amine, dithiol, thiol, isocyanate, and epoxy.

Specific examples of the monocarboxylic acid anhydride include succinic anhydride, phthalic anhydride, maleic anhydride, acetic anhydride, propionic anhydride, oxalic anhydride, and benzoic anhydride.

Examples of the dicarboxylic acid anhydride include carboxylic acid dianhydrides containing an aromatic ring, such as pyromellitic dianhydride, 4,4 ' -oxydiphthalic anhydride, 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, 2 ' -dimethyl-3, 3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, 5 ' -dimethyl-3, 3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, 2,3,3 ', 4 ' -biphenyltetracarboxylic dianhydride, 2 ', 3,3 ' -biphenyltetracarboxylic dianhydride and 3,3 ', 4,4 ' -diphenylethertetracarboxylic dianhydride, 1,2,3, 4-butanetetracarboxylic acid, 2,3, 5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, Aliphatic chain-containing carboxylic acid dianhydrides such as 1,2,3, 5-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, and 1,3,3a,4,5,9 b-hexahydro-5 (tetrahydro-2, 5-dioxo-3-furyl) naphtho [1,2-c ] furan-1, 3-dione.

Examples of the diol include ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 8-octanediol, 1, 9-nonanediol, 1, 4-cyclohexanediol, and diethylene glycol. When the diol is an aliphatic diol, the molecular chain length is preferably long in view of not impairing the flexibility of the resulting polysiloxane-polyalkylene glycol block copolymer.

Examples of the alcohols include methanol, ethanol, isopropanol, butanol, pentanol, hexanol, octanol, dodecanol, tetradecanol, hexadecanol, and octadecanol.

The monophenols are as described above.

Examples of the dihydric phenols include bisphenol a, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, and the like.

Examples of the diamine include ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 2-butylenediamine, 1, 3-butylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 3-methyl-1, 5-pentylenediamine, 1, 6-hexylenediamine, 2-dimethyl-1, 3-propylenediamine, 1, 8-octylenediamine, 1, 9-nonylenediamine, 1, 4-cyclohexanediamine, 1, 4-phenylenediamine, and 1, 4-xylylenediamine.

The amines are as described above. In addition, since there is a possibility that unreacted diamine or amine may cause poor fluidity if it remains, it is preferable to remove the unreacted diamine or amine by purification and drying after the reaction to such an extent that fluidity is not lowered.

Examples of the dithiol include ethanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, 1, 2-butanedithiol, 1, 3-butanedithiol, 1, 4-butanedithiol, 1, 5-pentanethiol, 3-methyl-1, 5-pentanethiol, 1, 6-hexanedithiol, 2-dimethyl-1, 3-propanedithiol, 1, 8-octanethiol, 1, 9-nonanedithiol, 1, 4-cyclohexanedithiol, 1, 4-benzenedithiol, and 1, 4-benzenedimethanethiol.

Examples of the thiol include 1-ethanethiol, 1-propanethiol (1-propylmercaptan), 2-propanethiol, 1-butanethiol, 2-butanethiol, 1-pentanethiol, 1-hexanethiol, 1-heptanethiol, 1-octanethiol, 1-nonanethiol, 1-cyclohexanethiol, benzenethiol, and benzylthiol.

Examples of the isocyanate include phenethylisocyanate, 1, 4-phenylene diisocyanate, and 1, 6-hexamethylene diisocyanate.

The epoxy is as described above.

When the number of functional groups of the copolymerization component (C) is 1, the molecular weight of the block copolymer to be obtained decreases as the addition amount increases, and when the number is 2, the molecular weight of the block copolymer increases.

The copolymerization component (C) is preferably reacted without using a metal catalyst as a reaction promoter. Further, a component capable of introducing a carboxyl group simultaneously is preferable in terms of improving dispersibility in an epoxy resin cured product. When the functional group of the polysiloxane (A) is a carboxylic anhydride group and the functional group of the polyalkylene glycol (B) is a hydroxyl group, examples thereof include monocarboxylic or dicarboxylic anhydrides.

When the functional group of the polysiloxane (a) is a carboxylic anhydride group and the polyalkylene glycol (B) is poly-1, 4-butanediol, and when the functional group of the polysiloxane (a) is a hydroxyl group and the polyalkylene glycol (B) is polypropylene glycol, the copolymerization component (C) includes pyromellitic dianhydride, 3 ', 4,4 ' -benzophenone tetracarboxylic dianhydride, 4,4 ' - (4,4 ' -isopropylidenediphenoxy) diphthalic anhydride, 4,4 ' -oxydiphthalic anhydride, 3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, and the like, from the viewpoint of improving reactivity by dissolving in the polysiloxane (a) and the poly-1, 4-butanediol or polypropylene glycol. Among them, pyromellitic dianhydride is preferable because it is easily soluble in the polysiloxane (a) and the polyalkylene glycol (B), is in a uniform state in the system, and allows the reaction to proceed without using a metal catalyst as a reaction accelerator.

Further, 1 kind of the copolymerization component (C) may be used, or 2 or more kinds may be used in combination.

The amount of the copolymerization component (C) to be added is not particularly limited, but is not limited to 100 mass%, preferably 40 mass% or less, more preferably 30 mass% or less, further preferably 20 mass% or less, and most preferably 10 mass% or less of the entire polysiloxane-polyalkylene glycol block copolymer, so as not to affect the physical properties of the polysiloxane-polyalkylene glycol block copolymer of the present invention. When the amount is more than this range, the flexibility of the resulting polysiloxane-polyalkylene glycol block copolymer is impaired, and the presence of unreacted copolymerization component (C) accelerates the curing reaction with the epoxy resin, resulting in a decrease in fluidity, which is not preferable.

In the case where polysiloxane (a) having a functional group and polyalkylene glycol (B) having a functional group do not directly react with each other, a method of adding copolymerization component (C) (hereinafter, sometimes referred to as copolymerization component (C ')) capable of reacting with both the functional group of polysiloxane (a) and the functional group of polyalkylene glycol (B) and reacting polysiloxane (a), polyalkylene glycol (B) and copolymerization component (C') may be used.

The copolymerization component (C') is not particularly limited as long as it is a component capable of reacting with both the polysiloxane having a functional group (a) and the polyalkylene glycol having a functional group (B) among the copolymerization components (C), and examples thereof include dicarboxylic anhydrides, diols, diphenols, diamines, dithiols, and diepoxides. When the functional groups of the polysiloxane (a) and the polyalkylene glycol (B) are hydroxyl groups, epoxy groups, amino groups, or thiol groups, dicarboxylic acid anhydrides are preferable in order to introduce carboxyl groups and improve dispersibility in the cured epoxy resin. Among them, preferred is a carboxylic anhydride selected from pyromellitic dianhydride, 3 ', 4,4 ' -benzophenone tetracarboxylic dianhydride, 4,4 ' - (4,4 ' -isopropylidenediphenoxy) diphthalic anhydride, 4,4 ' -oxydiphthalic anhydride, and 3,3 ', 4,4 ' -biphenyl tetracarboxylic dianhydride. The pyromellitic dianhydride is most preferable because flexibility can be imparted to the polysiloxane-polyalkylene glycol block copolymer obtained and copolymerization can be performed without using an organic solvent. The copolymerization component (C') may be used in 2 or more kinds. When the functional groups of the polysiloxane (a) and the polyalkylene glycol (B) are carboxylic anhydride groups, compounds selected from the group consisting of diols, diamines, dithiols, diphenols and epoxy compounds are preferable, and diols or diphenols are more preferable.

The content of the structure derived from the copolymerization component (C') in the polysiloxane-polyalkylene glycol block copolymer is preferably 30% by mass or less, assuming that the polysiloxane-polyalkylene glycol block copolymer is 100% by mass as a whole. If the content of the structure derived from the copolymerization component (C') is large, the low elastic modulus effect of the polysiloxane-polyalkylene glycol block copolymer becomes low. When the amount is small, the dispersibility in the cured epoxy resin is deteriorated. The content is preferably 25% by mass or less, more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 10% by mass or less.

The polysiloxane-polyalkylene glycol block copolymer of the present invention preferably has a structure represented by the general formula (3).

Here, n represents 5 to 100, m represents 3 to 300, and p represents the number of repeating units of 5 to 100. Furthermore, R¹Is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group. At R¹When the chain length of (b) is longer than the above, the polysiloxane-polyalkylene glycol block copolymer obtained is undesirably high in viscosity and poor in moldability when added to an epoxy resin. R¹Preferably any of propyl, ethyl and methyl, more preferably ethyl or methyl, most preferably methyl. In addition, all R¹May be different or the same. Z is a bonding portion formed by the reaction of the polysiloxane (a) having a functional group and the polyalkylene glycol having a functional group. When polysiloxane (a) and polyalkylene glycol (B) are directly reacted and bonded, a residue obtained by reacting X of polysiloxane (a) with Y of polyalkylene glycol (B) becomes bonding portion Z. In addition, in the case where the polysiloxane (a) and the polyalkylene glycol (B) are bonded via the copolymerization component (C ') without directly reacting, the residue obtained by reacting the above X of the polysiloxane (a), the above Y of the polyalkylene glycol (B), and the copolymerization component (C') becomes the bonding portion Z. As a result of this reaction, the binding moiety Z has a bond selected from an ester bond, an amide bond, and a thioester bond. Among these bonds, ester bonds and thioester bonds are preferable from the viewpoint of viscosity, and ester bonds are more preferable from the viewpoint of heat resistance. In addition, as a result of this reaction, Z also contains a newly formed carboxyl group. The carboxyl group can be a substituent including a carboxylic acid derivative by a reaction with the above-mentioned compound reactive with the carboxyl group. All Z's may be the same or different. R²Is selected from a single bond, a 2-valent aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms, anda 2-valent hydrocarbon ether group having 1 to 10 carbon atoms. Here, the single bond means R²Absent and silicon is directly bonded to Z. In addition, from the viewpoint of improving dispersibility in an epoxy resin cured product, R²Preferably butylene, propylene or ethylene, most preferably propylene or ethylene. R²Each may be the same or different. The 2-valent hydrocarbon ether group is preferably represented by- (CH)₂)_a-O-(CH₂)_b-represents, and 1. ltoreq. a + b. ltoreq.10. All R¹And R²Each may be the same or different.

The substituent containing a carboxylic acid derivative is a substituent generated by reacting a carboxyl group with a compound reactive with the carboxyl group, and examples thereof include an ester group, an amide group and the like. The ester group is a group represented by the structure represented by the following general formula (4).

Here, W is an alkyl group or an aromatic hydrocarbon group having 1 to 10 carbon atoms. W may have a hydroxyl group, an ether group and/or an ether amide group. Specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group and the like, and the alkyl group may have a straight chain structure or a branched chain structure. Further, as the aromatic hydrocarbon group, a phenyl group, a tolyl group, a naphthyl group, and the like can be given. Further, W may further have a substituent as long as it does not affect the low elastic modulus effect of the polysiloxane-polyalkylene glycol block copolymer, the good dispersibility in an epoxy resin cured product, and the flowability.

The amide group is a group having a structure represented by the following general formula (5).

W is as described above.

The content of the structure derived from polysiloxane in the polysiloxane-polyalkylene glycol block copolymer of the present invention is set to 100% by mass of the entire polysiloxane-polyalkylene glycol block copolymer, and the lower limit is 30% by mass or more, more preferably 35% by mass or more, further preferably 40% by mass or more, and most preferably 45% by mass or more. The upper limit of the content is 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less, and most preferably 55% by mass or less. When the content of the structure derived from polysiloxane is too small, even if a polysiloxane-polyalkylene glycol block copolymer is added to an epoxy resin to produce a cured product, the effect of low modulus of elasticity due to the addition of the polysiloxane-polyalkylene glycol block copolymer is poor. In addition, when the content of the structure derived from polysiloxane is too large, the polysiloxane-polyalkylene glycol block copolymer does not disperse well in the cured epoxy resin when added to the epoxy resin.

The content of the structure derived from polysiloxane in the polysiloxane-polyalkylene glycol block copolymer can be determined by dividing the weight of the polysiloxane (a) having a functional group at the time of synthesizing the block copolymer by the weight of all the raw materials. When a by-product is produced during the synthesis of the block copolymer, the weight of the by-product produced is calculated by subtracting the weight of all the raw materials. That is, the content of the structure derived from the polysiloxane can be determined by the following formula.

[ number 1]

The polysiloxane-polyalkylene glycol block copolymer of the present invention has a carboxyl group content of 0.1mmol/g to 0.75 mmol/g. The lower limit of the carboxyl group content is more preferably 0.2mmol/g or more, still more preferably 0.3mmol/g or more, particularly preferably 0.4mmol/g or more, and most preferably 0.45mmol/g or more. The upper limit value is more preferably 0.7mmol/g or less, still more preferably 0.65mmol/g or less, and particularly preferably 0.6mmol/g or less.

When the carboxyl group content is more than this range, the effect of reducing the modulus of elasticity is not preferable when the polysiloxane-polyalkylene glycol block copolymer of the present invention is added to produce a cured epoxy resin. When the carboxyl group content is less than this range, dispersibility in the cured epoxy resin is lowered, and the polysiloxane-polyalkylene glycol block copolymer is coarsely dispersed in the cured epoxy resin, which is not preferable.

The carboxyl group content can be determined by a known titration method. For example, the polysiloxane-polyalkylene glycol block copolymer is dissolved in toluene or tetrahydrofuran, phenolphthalein is used as an indicator, and titration is performed with 0.1mol/L alcoholic potassium hydroxide, and the obtained value is calculated.

The weight average molecular weight (M) of the polysiloxane-polyalkylene glycol block copolymer of the present invention_w) The lower limit of the amount of the polysiloxane-polyalkylene glycol block copolymer is preferably 5,000 or more, more preferably 6,000 or more, more preferably 8,000 or more, more preferably 10,000 or more, more preferably 15,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more, from the viewpoint of mechanical properties and molding processability of a cured epoxy resin to which the polysiloxane-polyalkylene glycol block copolymer is added. The upper limit value is preferably 500,000 or less, more preferably 200,000 or less, more preferably 150,000 or less, still more preferably 100,000 or less, and most preferably 80,000 or less. When the weight average molecular weight is less than this range, the effect of lowering the modulus of elasticity of an epoxy resin cured product to which the polysiloxane-polyalkylene glycol block copolymer is added is deteriorated. When the weight average molecular weight is more than this range, the epoxy resin composition added to the epoxy resin is undesirably high in viscosity, which causes the occurrence of cracks due to the penetration of fine parts during molding of the sealing material.

The weight average molecular weight of the polysiloxane-polyalkylene glycol block copolymer herein means a weight average molecular weight obtained by gel permeation chromatography using Tetrahydrofuran (THF) as a solvent and converting the weight average molecular weight into a standard sample using polymethyl methacrylate.

In the case where Tetrahydrofuran (THF) was used as a solvent and measurement was impossible, N-dimethylformamide was used as a solvent, and in the case where measurement was impossible despite this, hexafluoroisopropanol was used.

Number average molecular weight (M) of the polysiloxane-polyalkylene glycol block copolymer of the present invention_n) The lower limit value is not particularly limited, but from the viewpoint of mechanical properties and molding processability of an epoxy resin cured product to which the polysiloxane-polyalkylene glycol block copolymer is added, it is 1,000 or more, preferably 2,000 or more, more preferably 5,000 or more, further preferably 10,000 or more, further preferably 15,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more. The upper limit thereof is preferably 500,000 or less, more preferably 200,000 or less, more preferably 150,000 or less, further preferably 100,000 or less, and most preferably 80,000 or less. When the weight average molecular weight is less than this range, the effect of lowering the modulus of elasticity of an epoxy resin cured product to which the polysiloxane-polyalkylene glycol block copolymer is added is deteriorated. When the weight average molecular weight is more than this range, the epoxy resin composition added to the epoxy resin is undesirably high in viscosity, which causes the occurrence of cracks due to the penetration of fine parts during molding of the sealing material. The number average molecular weight can be determined by gel permeation chromatography in the same manner as the weight average molecular weight.

Further, the molecular weight distribution (M) of the polysiloxane-polyalkylene glycol block copolymer of the present invention_w/M_n) Preferably 5 or less, more preferably 3 or less, and still more preferably 2 or less. The lower limit of the molecular weight distribution is theoretically 1. In addition, molecular weight distribution (M)_w/M_n) Weight average molecular weight (M) determined as described above using gel permeation chromatography_w) And number average molecular weight (M)_n) And (6) calculating.

The polysiloxane-polyalkylene glycol block copolymer has soft 2 polymer skeletons and a carboxyl group content of 0.1-0.75 mmol/g, so that when the polysiloxane-polyalkylene glycol block copolymer is added to an epoxy resin, a cured product of the polysiloxane-polyalkylene glycol block copolymer can show a remarkable low elastic modulus effect. The polysiloxane-polyalkylene glycol block copolymer of the present invention can be well dispersed in an epoxy resin cured product, so that there is no variation in material properties, and by adding a small amount of the polysiloxane-polyalkylene glycol block copolymer, the epoxy resin cured product can be effectively reduced in elastic modulus, and internal stress can be alleviated.

The method for producing a polysiloxane-polyalkylene glycol block copolymer of the present invention performs the following step (2) after the following step (1).

Step (1): a step of reacting a polysiloxane (a) having a functional group selected from a carboxylic acid anhydride group, a hydroxyl group, an epoxy group, an amino group, and a thiol group with a polyalkylene glycol (B) having a functional group selected from a carboxylic acid anhydride group, a hydroxyl group, an amino group, an epoxy group, and a thiol group to obtain a polysiloxane-polyalkylene glycol block copolymer intermediate;

step (2): is a step of reacting a carboxyl group of the intermediate polysiloxane-polyalkylene glycol block copolymer obtained in the step (1) with a compound having reactivity with a carboxyl group selected from orthoesters,At least 1 compound selected from the group consisting of oxazolines, epoxies, alcohols, monophenols, haloalkanes, and alkyl carbonates.

According to the conventional method of introducing a carboxyl group into a copolymer, since a functional group as a reaction residue is introduced into a molecular chain, 2 carboxyl groups are introduced into both ends of the molecular chain, that is, 1 molecular chain. The polysiloxane-polyalkylene glycol block copolymer of the present invention may contain at least 3 or more functional groups in 1 molecular chain by reacting polysiloxane (a) having a functional group and polyalkylene glycol (B) having a functional group. More preferably 5 or more, still more preferably 10 or more, and still more preferably 20 or more. That is, the polysiloxane-polyalkylene glycol block copolymer of the present invention preferably has a product of number average molecular weight and carboxyl group content of more than 2. More preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 20 or more.

Examples of the method for reacting the polysiloxane (a) having a functional group and the polyalkylene glycol (B) having a functional group include a method in which the polysiloxane (a) and the polyalkylene glycol (B) having a functional group are mixed and heated to react with each other. If necessary, the reaction may be carried out in an organic solvent. If necessary, the reaction may be carried out under a nitrogen atmosphere, or under a reduced pressure to promote the reaction.

The mixing ratio of the functional group-containing polysiloxane (a) and the functional group-containing polyalkylene glycol (B) can be appropriately adjusted, but when the functional group-containing polysiloxane (a) and the functional group-containing polyalkylene glycol (B) are directly reacted and bonded, the mixing ratio is preferably such that the stoichiometric equivalent ratio is 0.1 to 10. Here, the stoichiometric equivalent ratio refers to a ratio of the number of moles of the functional group contained in the polyalkylene glycol (B) to the number of moles of the functional group contained in the polysiloxane (a). The equivalent ratio is more preferably 0.2 to 5, still more preferably 0.5 to 3, most preferably 0.8 to 1.5, and particularly preferably 1.

On the other hand, when the polysiloxane (a) having a functional group and the polyalkylene glycol (B) having a functional group do not directly react with each other, and the copolymerization component (C) reacts with the polysiloxane (a) and the polyalkylene glycol (B) to bond them, the equivalent ratio of the number of moles of the functional group contained in the copolymerization component (C) to the total number of moles of the functional groups contained in the polysiloxane (a) and the polyalkylene glycol (B) is more preferably 0.2 to 5, still more preferably 0.5 to 3, still more preferably 0.8 to 1.5, and most preferably 1.

When the block copolymer is synthesized so that the content of the structure derived from the polysiloxane (a) contained in 100 mass% of the obtained polysiloxane-polyalkylene glycol block copolymer is 30 mass% or more and 70 mass% or less, it is preferable to adjust the addition ratio of the raw materials and react them.

When an organic solvent is used for the reaction, the organic solvent is preferably a good solvent of the polysiloxane (a) having a functional group and the polyalkylene glycol (B) having a functional group. Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, benzene, and 2-methylnaphthalene; ester solvents such as ethyl acetate, methyl acetate, butyl propionate, butyl butyrate, and ethyl acetoacetate; halogenated hydrocarbon solvents such as chloroform, bromoform, dichloromethane, carbon tetrachloride, 1, 2-dichloroethane, 1,1, 1-trichloroethane, chlorobenzene, 2, 6-dichlorotoluene, 1,1,1,3,3, 3-hexafluoroisopropanol and the like; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl butyl ketone; alcohol solvents such as methanol, ethanol, 1-propanol, and 2-propanol; carboxylic acid solvents such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; anisole, diethyl ether, tetrahydrofuran, diisopropyl ether, diEther solvents such as alkane, diglyme, dimethoxyethane and the like; or mixtures thereof.

Among them, toluene, xylene or ethyl acetate is preferable from the viewpoint of the balance between the reaction rate and the solvent removal after the reaction. These organic solvents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

In addition, when the reaction is carried out in an organic solvent, the organic solvent can be removed by a known method such as heating, pressure reduction, reprecipitation, or the like, and the product can be purified. In order to remove the organic solvent, a plurality of steps may be combined.

However, the case of not using an organic solvent is preferable because productivity is improved in terms of not requiring a purification step for removing the organic solvent and simplifying a production step, and also in terms of enabling a high reaction temperature and increasing a reaction rate even in a system not using a metal catalyst as a reaction promoter.

The temperature at which the polysiloxane having a functional group (a) and the polyalkylene glycol having a functional group (B) are reacted is not particularly limited, but is preferably 220 ℃ or less, more preferably 200 ℃ or less, further preferably 180 ℃ or less, and particularly preferably 150 ℃ or less, in order to suppress side reactions and decomposition of the polymer. Further, when the reaction is carried out at room temperature or lower, it is difficult to store the reaction stably at room temperature, and therefore the reaction is preferably not carried out at room temperature or lower. The lower limit of the temperature at which the reaction is carried out is preferably 50 ℃ or higher, more preferably 70 ℃ or higher, and still more preferably 100 ℃ or higher.

In addition, although a reaction accelerator or the like may be added during the reaction, the polysiloxane (a) having a functional group and the polyalkylene glycol (B) having a functional group can be easily reacted without adding a reaction accelerator.

From the viewpoint of productivity, the reaction time is preferably within 20 hours, more preferably within 15 hours, and still more preferably within 10 hours.

Next, the carboxyl group of the block copolymer intermediate obtained in this way is reacted with a compound reactive to a carboxyl group to control the carboxyl group content to a desired level, thereby obtaining the polysiloxane-polyalkylene glycol block copolymer of the present invention. By this reaction, a part of the carboxyl group is blocked to generate a substituent including a carboxylic acid derivative. The compound having reactivity with a carboxyl group is as described above.

The temperature at which the compound reactive with a carboxyl group is reacted with a carboxyl group is not particularly limited, and depends on the compound to be used, and is preferably 220 ℃ or lower, more preferably 200 ℃ or lower, further preferably 180 ℃ or lower, and particularly preferably 150 ℃ or lower. Further, when the reaction proceeds at room temperature or lower, it is difficult to store the reaction stably at room temperature, and therefore the reaction does not proceed at room temperature or lower. The lower limit of the temperature at which the reaction is carried out is preferably 50 ℃ or higher, more preferably 70 ℃ or higher, and still more preferably 100 ℃ or higher. The reaction may be carried out under reduced pressure. Further, although a catalyst or a condensing agent may be added, it is preferable not to add it because a step such as purification is added to remove them and the production efficiency is lowered.

When reacting with a compound having reactivity with a carboxyl group, the same solvent as that used in the reaction of the polysiloxane having a functional group (a) with the polyalkylene glycol having a functional group (B) can be used. In addition, when the reaction is carried out in an organic solvent, the organic solvent can be removed by a known method such as heating, pressure reduction, reprecipitation, or the like, and the product can be purified. In order to remove the organic solvent, a plurality of steps may be combined.

However, the case of not using an organic solvent is preferable because productivity is improved in terms of not requiring a purification step for removing the organic solvent and simplifying a production step, and also in terms of enabling a high reaction temperature and increasing a reaction rate even in a system not using a metal catalyst as a reaction promoter.

The lower limit of the drying temperature for removing the organic solvent and by-products generated in the reaction is not particularly limited, but is preferably 50 ℃ or higher, more preferably 80 ℃ or higher, and still more preferably 100 ℃ or higher, in order to remove efficiently in a short time.

The epoxy resin composition of the present invention is obtained by mixing an epoxy resin described below with the block copolymer of the present invention, and means a mixture before a curing reaction is carried out.

The amount of the polysiloxane-polyalkylene glycol block copolymer contained in the epoxy resin composition of the present invention is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, even more preferably 0.5 to 30 parts by mass, and even more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the epoxy resin. By including the polysiloxane-polyalkylene glycol block copolymer in the epoxy resin composition in the above range, the internal stress can be relaxed efficiently in an epoxy resin cured product obtained by curing the epoxy resin composition.

As the epoxy resin, there is no particular limitation, and for example, a glycidyl ether type epoxy resin obtained from a compound having a hydroxyl group and epichlorohydrin, a glycidyl amine type epoxy resin obtained from a compound having an amino group and epichlorohydrin, a glycidyl ester type epoxy resin obtained from a compound having a carboxyl group and epichlorohydrin, an alicyclic epoxy resin obtained by oxidizing a compound having a double bond, or an epoxy resin in which 2 or more types of groups selected from them are mixed in the molecule, or the like is used.

Specific examples of the glycidyl ether type epoxy resin include a bisphenol a type epoxy resin obtained by a reaction of bisphenol a and epichlorohydrin, a bisphenol F type epoxy resin obtained by a reaction of bisphenol F and epichlorohydrin, a bisphenol S type epoxy resin obtained by a reaction of 4,4 '-dihydroxydiphenylsulfone and epichlorohydrin, a biphenyl type epoxy resin obtained by a reaction of 4, 4' -biphenol and epichlorohydrin, a resorcinol type epoxy resin obtained by a reaction of resorcinol and epichlorohydrin, a phenol novolac type epoxy resin obtained by a reaction of phenol and epichlorohydrin, other polyethylene glycol type epoxy resins, polypropylene glycol type epoxy resins, and positional isomers thereof, substituted bodies substituted with alkyl groups or halogens.

Commercially available products of bisphenol a type epoxy resins include "jER" (registered trademark) 825, "jER" (registered trademark) 826, "jER" (registered trademark) 827, "jER" (registered trademark) 828 (manufactured by mitsubishi ケミカル, or more), "エピクロン" (registered trademark) 850 (manufactured by DIC (registered trademark), "エポトート" (registered trademark) YD-128 (manufactured by seikagaku corporation), d.e.r-331 (trademark) (manufactured by ダ ウ ケミカル), "Bakelite" (registered trademark) EPR154, "Bakelite" (registered trademark) EPR162, "Bakelite" (registered trademark) EPR172, "Bakelite" (registered trademark) EPR173, and "Bakelite" (registered trademark) EPR174 (manufactured by Bakelite AG, or more).

Examples of commercially available products of bisphenol F type epoxy resins include "jER" (registered trademark) 806, "jER" (registered trademark) 807, "jER" (registered trademark) 1750 (see above, manufactured by mitsubishi ケミカル (ltd.), "エピクロン" (registered trademark) 830 (manufactured by DIC (ltd.), "エポトート" (registered trademark) YD-170, "エポトート" (registered trademark) YD-175 (manufactured by seikagaku chemical corporation), "Bakelite" (registered trademark) EPR169 (manufactured by Bakelite AG), "アラルダイト" (registered trademark) GY281, "アラルダイト" (registered trademark) 282 GY, and "アラルダイト" (registered trademark) GY285 (see above, manufactured by ハンツマン, アドバンスト, マテリアルズ).

Examples of the biphenyl type epoxy resin include "jER" (registered trademark) YX4000, "jER" (registered trademark) YX4000K, "jER" (registered trademark) YX4000H, "jER" (registered trademark) YX4000HK (manufactured by mitsubishi ケミカル (ltd.)), and the like.

Examples of commercially available products of resorcinol-based epoxy resins include "デナコール" (registered trademark) EX-201 (manufactured by ナガセケムテックス K.K.).

Commercially available products of phenol novolac epoxy resins include "jER" (registered trademark) 152, "jER" (registered trademark) 154 (see above, mitsubishi ケミカル (product of japan), and "エピクロン" (registered trademark) 740 (see DIC (product of DIC)), EPN179, and EPN180 (see above, products of ハンツマン, アドバンスト, マテリアルズ).

Specific examples of the glycidyl amine type epoxy resin include tetraglycidyl diaminodiphenylmethane, glycidyl compounds of aminophenol, glycidyl anilines, and glycidyl compounds of xylylenediamine.

Examples of commercially available products of tetraglycidyl diaminodiphenylmethane include "スミエポキシ" (registered trademark) ELM434 (manufactured by sumitomo chemical corporation), "アラルダイト" (registered trademark) MY720, "アラルダイト" (registered trademark) MY721, "アラルダイト" (registered trademark) MY9512, "アラルダイト" (registered trademark) MY9612, "アラルダイト" (registered trademark) MY9634, "アラルダイト" (registered trademark) MY9663 (manufactured by ハンツマン, アドバンスト, マテリアルズ), and "jER" (registered trademark) 604 (manufactured by mitsubishi ケミカル corporation), "Bakelite" (registered trademark) EPR494, "Bakelite" (registered trademark) EPR495, "Bakelite" (registered trademark) EPR496, and "Bakelite" (registered trademark) EPR497 (manufactured by AG, Bakelite co.).

Commercially available products of glycidyl compounds of aminophenol include "jER" (registered trademark) 630 (manufactured by mitsubishi ケミカル corporation), "アラルダイト" (registered trademark) MY0500, "アラルダイト" (registered trademark) MY0510 (manufactured by ハンツマン, アドバンスト, マテリアルズ), and "スミエポキシ" (registered trademark) ELM120 and "スミエポキシ" (registered trademark) ELM100 (manufactured by sumitomo chemical corporation).

Commercially available glycidyl anilines include GAN, GOT (manufactured by japan chemical corporation), and "Bakelite" (registered trademark) EPR493 (manufactured by Bakelite AG).

Examples of the glycidyl compound of xylylenediamine include TETRAD-X (registered trademark) (manufactured by Mitsubishi gas chemical corporation).

Specific examples of the glycidyl ester type epoxy resin include diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl isophthalate, diglycidyl dimer acid, and various isomers thereof.

Commercially available diglycidyl phthalate esters include "エポミック" (registered trademark) R508 (manufactured by Mitsui chemical Co., Ltd.) and "デナコール" (registered trademark) EX-721 (manufactured by ナガセケムテックス Co., Ltd.).

Commercially available products of diglycidyl hexahydrophthalate include "エポミック" (registered trademark) R540 (manufactured by Mitsui chemical Co., Ltd.), AK-601 (manufactured by Nippon chemical Co., Ltd.), and the like.

Examples of commercially available dimer acid diglycidyl ester include "jER" (registered trademark) 871 (manufactured by mitsubishi ケミカル corporation) and "エポトート" (registered trademark) YD-171 (manufactured by shinkanji chemical corporation).

Commercially available alicyclic epoxy resins include "セロキサイド" (registered trademark) 2021P (manufactured by corporation ダイセル), "CY 179 (manufactured by ハンツマン, アドバンスド, マテリアルズ)," セロキサイド "(registered trademark) 2081 (manufactured by corporation ダイセル), and" セロキサイド "(registered trademark) 3000 (manufactured by corporation ダイセル).

The epoxy resin is preferably a resin selected from the group consisting of a biphenyl type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin and a bisphenol S type epoxy resin, more preferably a biphenyl type epoxy resin or a bisphenol a type epoxy resin, and still more preferably a biphenyl type epoxy resin, from the viewpoint of heat resistance, toughness and low reflow property. The epoxy resin may be used alone, or 2 or more kinds thereof may be used in combination.

A curing agent and/or a curing accelerator may be added to the epoxy resin composition.

Examples of the epoxy resin curing agent include aliphatic polyamine curing agents such as diethylenetriamine and triethylenetetramine;alicyclic polyamine-based curing agents such as enediamine (mendeniamine) and isophoronediamine; aromatic polyamine-based curing agents such as diaminodiphenylmethane and m-phenylenediamine; acid anhydride curing agents such as polyamide, modified polyamine, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride; polyphenol curing agents such as phenol novolac resins and phenol aralkyl resins; anionic catalysts such as polythiols, 2,4, 6-tris (dimethylaminomethyl) phenol, 2-ethyl-4-methylimidazole, and 2-phenyl-4-methylimidazole; cationic catalysts such as boron trifluoride/monoethylamine complexes; and potential curing agents such as dicyandiamide, aromatic diazonium salts (aromatic diazo salts), and molecular sieves.

In particular, in order to obtain an epoxy resin cured product having excellent mechanical properties, it is preferable to use a curing agent selected from aromatic amine curing agents, acid anhydride curing agents, and polyphenol curing agents.

Specific examples of the aromatic amine curing agent include various derivatives such as m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylylenediamine, diphenyl-p-diphenylamine, and alkyl substituents thereof, and isomers having amino groups at different positions.

Specific examples of the acid anhydride curing agent include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, dodecenylsuccinic anhydride, and benzophenone tetracarboxylic dianhydride.

Specific examples of the polyphenol curing agent include phenol aralkyl resins, 1-naphthol aralkyl resins, o-cresol novolac epoxy resins, dicyclopentadiene phenol resins, terpene phenol resins, naphthol novolac type resins, and the like.

The optimum value of the addition amount of the curing agent varies depending on the kinds of the epoxy resin and the curing agent, but the stoichiometric equivalent ratio of the curing agent is preferably 0.5 to 1.4, more preferably 0.6 to 1.4, relative to all epoxy groups contained in the epoxy resin composition. When the equivalent ratio is less than 0.5, the curing reaction does not sufficiently occur, poor curing may occur, or a long time may be required for the curing reaction. If the equivalent ratio is more than 1.4, the curing agent that is not consumed during curing becomes a defect, and the mechanical properties may be degraded.

The curing agent may be used in any form of a monomer or oligomer, and may be in any form of powder or liquid when mixed. These curing agents may be used alone, or 2 or more of them may be used in combination. Further, a curing accelerator may be used in combination.

As the curing accelerator, there can be used an amine compound-based curing accelerator represented by1, 8-diazabicyclo (5.4.0) undecene-7; imidazole compound-based curing accelerators represented by 2-methylimidazole and 2-ethyl-4-methylimidazole; phosphorus compounds represented by triphenyl phosphite as a curing accelerator. Among these, a phosphorus compound-based curing accelerator is most preferable.

Various additives such as flame retardants other than the epoxy resin and the block copolymer, fillers, colorants, and mold release agents may be added to the epoxy resin composition of the present invention as needed.

The filler is not particularly limited, and powder or fine particles of fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, aluminum nitride, boron nitride, beryllium oxide, zirconia, or the like can be used. These fillers may be used alone or in combination of 2 or more. Among them, fused silica is preferably used from the viewpoint of reducing the linear expansion coefficient. The shape of the filler is preferably spherical from the viewpoint of fluidity and abrasion resistance during molding.

The amount of the filler is preferably 20 to 2000 parts by mass, more preferably 50 to 2000 parts by mass, further preferably 100 to 2000 parts by mass, particularly preferably 100 to 1000 parts by mass, and most preferably 500 to 800 parts by mass, based on 100 parts by mass of the epoxy resin, from the viewpoints of reduction in moisture absorption rate, reduction in linear expansion coefficient, and improvement in strength.

Examples of the other additives include carbon black, calcium carbonate, titanium oxide, silica, aluminum hydroxide, glass fiber, hindered amine-based deterioration inhibitor, hindered phenol-based deterioration inhibitor, and the like.

These additives are preferably added at a stage before curing of the epoxy resin composition, and may be added in the form of any of powder, liquid, and slurry.

The epoxy resin composition of the present invention has good fluidity and excellent workability. When the epoxy resin composition is used for a semiconductor sealing material, the epoxy resin composition cannot be filled up to the fine portion when the flowability is poor, and the epoxy resin composition may cause voids and damage to the package. The block copolymer of the present invention can provide an epoxy resin composition which, when added to an epoxy resin, has a small increase in viscosity due to the addition and is excellent in fluidity. In addition, 2 or more block copolymers may be added to the epoxy resin composition.

The polysiloxane-polyalkylene glycol block copolymer of the present invention has a polysiloxane skeleton which is incompatible with an epoxy resin but has excellent flexibility, and a polyalkylene glycol skeleton which is compatible with an epoxy resin and has excellent flexibility, and therefore exhibits good dispersibility in a cured epoxy resin and a low modulus of elasticity effect. The cured epoxy resin can be produced by a known method. For example, a method of mixing an epoxy resin, a curing agent, a curing accelerator, various additives, and a filler and curing the mixture by heating is exemplified.

From the viewpoint of work efficiency in the production of the sealing material, the fluidity of the epoxy resin composition is preferably low when a cured product is produced. Due to impurities contained in the block copolymer, the viscosity of the epoxy resin composition may increase and the flowability may decrease. In the case of such impurities, it is preferable to purify and dry the impurities so as to be within a range that does not reduce the fluidity. In particular, impurities having nitrogen atoms cause a decrease in fluidity, and examples thereof include amines.

The fluidity of the epoxy resin composition can be evaluated by viscosity measurement using a rheometer. Specifically, the viscosity at a temperature of 200 ℃ was measured using a rheometer for the viscosity of an epoxy resin composition containing 15 parts by mass of a polysiloxane-polyalkylene glycol block copolymer per 100 parts by mass of the epoxy resin. In addition, in the case of containing an epoxy resin curing agent, the viscosity of an epoxy resin composition containing 15 parts by mass of a polysiloxane-polyalkylene glycol block copolymer per 100 parts by mass of the total of the epoxy resin and the epoxy resin curing agent was measured. In the same manner, the viscosity at a temperature of 200 ℃ of the epoxy resin containing no block copolymer was measured. The viscosity at 200 ℃ measured in this manner was evaluated for fluidity as the ratio of the viscosity of an epoxy resin composition containing 15 parts by mass of a block copolymer to the viscosity of an epoxy resin not containing a block copolymer to the increase in the viscosity of 100 parts by mass of the epoxy resin composition. The ratio of increase in viscosity is preferably 15 times or less, more preferably 10 times or less, particularly preferably 8 times or less, and most preferably 5 times or less. The rising ratio of the viscosity is preferably small. The lower limit of the viscosity is theoretically 1 time or more. When the increase ratio of the viscosity is large, the obtained epoxy resin composition is not preferable because the fluidity is poor, and the epoxy resin composition cannot penetrate to the fine portion at the time of molding the sealing material, thereby causing cracks.

The epoxy resin composition of the present invention can be produced by adding the block copolymer to an epoxy resin and, if necessary, a curing agent, and kneading the mixture using a generally known kneader. Examples of the kneading machine include a three-roll kneading machine, a self-revolving mixer, and a planetary mixer.

The epoxy resin cured product of the present invention is obtained by a curing reaction of the epoxy resin composition.

If necessary, a temperature may be applied to the epoxy resin composition for the curing reaction to obtain a cured epoxy resin. The temperature at this time is preferably room temperature to 250 ℃, more preferably 50 to 200 ℃, further preferably 70 to 190 ℃, and particularly preferably 100 to 180 ℃. Further, a temperature raising program of temperature may be applied as necessary. The rate of temperature rise at this time is not particularly limited, but is preferably 0.5 to 20 ℃/min, more preferably 0.5 to 10 ℃/min, and still more preferably 1 to 5 ℃/min.

In addition, the pressure during curing is preferably 1 to 100kg/cm²More preferably 1 to 50kg/cm²More preferably 1 to 20kg/cm²Particularly preferably 1 to 5kg/cm²。

The polysiloxane-polyalkylene glycol block copolymer of the present invention can be dispersed well in an epoxy resin cured product. Whether or not the resin plate is well dispersed (well dispersed) can be determined by dyeing the cured resin plate with ruthenium tetroxide, observing the cross section thereof with a transmission electron microscope, and confirming the result with the obtained photograph. The polysiloxane region structure is dyed by dyeing with ruthenium tetroxide. The polysiloxane region structure is preferably such that the finer the average region structure diameter, the more excellent the dispersibility. The average domain structure diameter of the polysiloxane domain structure can be calculated by specifying the diameters of arbitrary 100 domain structures in the Transmission Electron Microscope (TEM) photograph and calculating the arithmetic mean according to the following formula. When the domain structure is not a perfect sphere, the maximum diameter of the domain structure is defined as the diameter thereof.

[ number 2]

In addition, Ri: diameter of each of the domain structures, n: determination numbers 100, Dn: average area structure diameter.

The average domain structure diameter of the polysiloxane domain structure in the epoxy resin cured product obtained by the method is preferably 50 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, particularly preferably 3 μm or less, significantly preferably 1 μm or less, and most preferably 500nm or less.

When the measurement of the dispersion state using the above method is difficult, the dispersion state of the polysiloxane-polyalkylene glycol block copolymer in the cured epoxy resin can be confirmed using energy dispersive X-ray analysis (EDX). Specifically, the dispersion state of the polysiloxane-polyalkylene glycol block copolymer was judged by observing the cross section of the cured epoxy resin to which polysiloxane was added by EDX and mapping with silicon.

The semiconductor sealing material of the present invention comprises the epoxy resin cured product of the present invention. The epoxy resin cured product of the present invention functions as a low-stress agent by the polysiloxane-polyalkylene glycol block copolymer, and is used as a material suitable for a semiconductor sealing material. The semiconductor sealing material herein refers to a material that is sealed in order to protect electronic components such as semiconductor elements from external stimuli.

As described above, the polysiloxane-polyalkylene glycol block copolymer of the present invention is obtained by the reaction of polysiloxane (a) having a functional group and polyalkylene glycol (B) having a functional group, and can have a high molecular weight and a large amount of functional groups in the molecule, thereby having very excellent dispersibility in an epoxy resin. Further, by controlling the carboxyl group content to a desired level by reacting the carboxyl group of the block copolymer intermediate obtained in this way with a compound reactive with a carboxyl group, it is possible to exhibit a significant effect of reducing the elastic modulus of the cured product when added to an epoxy resin. The epoxy resin composition comprising the polysiloxane-polyalkylene glycol block copolymer of the present invention and an epoxy resin has excellent flowability, and the decrease in flowability caused by the addition of the block copolymer is small, and the workability is excellent. Further, with respect to the epoxy resin cured product obtained by curing the epoxy resin composition, the added block copolymer is finely dispersed, and bleeding is also suppressed, and not only is the low elastic modulus of the epoxy resin cured product exhibited, but also the toughness-improving effect is exhibited. Thus, the block copolymer of the present invention is extremely useful as a low-stress agent for epoxy resins.

Examples

Next, the present invention will be described in further detail based on examples. However, the present invention is not limited to these examples. In the examples, the measurement methods used are as follows.

(1) Determination of weight average molecular weight

The weight average molecular weights of the polysiloxane-polyalkylene glycol block copolymer, the polysiloxane (a) having a functional group, and the polyalkylene glycol (B) having a functional group were measured by gel permeation chromatography under the following conditions, and the molecular weights were calculated by comparing with a calibration curve obtained from polymethyl methacrylate.

The device comprises the following steps: LC-20AD series manufactured by Shimadzu corporation

Column: showa Denko K.K. KF-806 Lx 2

Flow rate: 1.0mL/min

Mobile phase: tetrahydrofuran (THF)

And (3) detection: differential refractometer

Column temperature: at 40 ℃.

(2) Quantification of carboxyl content

0.5g of a polysiloxane-polyalkylene glycol block copolymer was dissolved in 10g of tetrahydrofuran, and the content of carboxyl groups was quantified by titration with 0.1mol/L of alcoholic potassium hydroxide using phenolphthalein as an indicator.

(3) Method for calculating content of structure derived from polysiloxane (A)

The content of the structure derived from the polysiloxane in the polysiloxane-polyalkylene glycol block copolymer is determined by dividing the weight of the polysiloxane (a) having a functional group at the time of synthesizing the block copolymer by the total weight of all the raw materials. When a by-product is generated by the reaction of the block copolymer intermediate with a compound reactive with a carboxyl group, the weight of the by-product is subtracted from the total weight of all raw materials. That is, the content of the structure derived from the polysiloxane (a) is calculated by the following formula.

[ number 3]

(4) Viscosity measurement

The viscosity of the epoxy resin shown in each example was measured under the following conditions using a rheometer (MCR 501 manufactured by Anton Paar), and the viscosity at 200 ℃. Next, the viscosity at 200 ℃ of the epoxy resin composition containing 15 parts by mass of the block copolymer based on 100 parts by mass of the total of the epoxy resin and the epoxy resin curing agent was measured in the same manner. The fluidity was evaluated from the ratio of the increase in viscosity of the epoxy resin composition containing 15 parts by mass of the block copolymer to the viscosity of the epoxy resin not containing the block copolymer.

A clamp: phi 25mm parallel plate

Frequency: 0.5Hz

Strain: 100 percent

Spacing: 1mm

Measuring temperature: 70-220 deg.C

Temperature rise rate: 10 ℃/min

Atmosphere: nitrogen gas.

(5) Determination of flexural modulus of elasticity and breaking Strain

A test piece was obtained by cutting an epoxy resin cured product in which a polysiloxane-polyalkylene glycol block copolymer was dispersed into a width of 10mm, a length of 80mm, and a thickness of 4 mm. A3-point bending test was carried out using an テンシロン universal tester (Tensairon TRG-1250, manufactured by エー, アンド, デイ) under the conditions of an inter-fulcrum distance of 64mm and a test speed of 2 mm/min in accordance with JIS K7171(2008), and the flexural modulus and the strain at break were measured. The measurement temperature was set to room temperature (23 ℃), and the number of measurements was determined as n-5.

(6) Measurement of average Domain Structure diameter of polysiloxane Domain Structure in cured Material

The cured epoxy resin in which the polysiloxane-polyalkylene glycol block copolymer was dispersed was dyed with ruthenium tetroxide, a photograph was obtained from the cross section thereof by a transmission electron microscope, and the diameter of any 100 polysiloxane domain structures was measured from the photograph and calculated according to the following formula.

[ number 4]

In addition, Ri: diameter of each of the domain structures, n: determination numbers 100, Dn: average area structure diameter.

(Synthesis of intermediate of polysiloxane-polyalkylene glycol Block copolymer)

[ Synthesis example 1]

A100 mL separable flask was charged with 10.0g of both-end maleic anhydride-modified silicone oil (X-22-168 AS, manufactured by shin-Etsu chemical Co., Ltd., weight average molecular weight 1300, 5% weight loss temperature 299 ℃ C.) and 10.0g of poly-1, 4-butanediol (polytetrahydrofuran (Polytetramethylene oxide)1,000, weight average molecular weight 2700, 5% weight loss temperature 275 ℃ C.) to replace with nitrogen. Then, it was heated to 120 ℃ to react for 8 hours, to obtain a polysiloxane-polyalkylene glycol block copolymer intermediate. The obtained intermediate polysiloxane-polyalkylene glycol block copolymer had a content of the structure derived from polysiloxane (A) of 50 mass%, a carboxyl group content of 1.01mmol/g, a number average molecular weight of 27,800 and a weight average molecular weight of 49,200. The results are shown in table 1.

[ Synthesis example 2]

A100 mL separable flask was charged with 10g of both-terminal hydroxyl-modified silicone oil (KF-6001, manufactured by shin-Etsu chemical Co., Ltd., weight-average molecular weight 3000, 5% weight loss temperature 298 ℃ C.) and 8.0g of polypropylene glycol (polypropylene glycol, glycol type, 2000, weight-average molecular weight 3350, manufactured by Wako pure chemical industries Co., Ltd., weight loss temperature 296 ℃ C.) to obtain a homogeneous solution. Next, 2.0g of pyromellitic dianhydride (manufactured by Tokyo chemical industry Co., Ltd.) was added thereto, and nitrogen substitution was performed. Then, it was heated to 160 ℃ to react for 8 hours, to obtain a polysiloxane-polyalkylene glycol block copolymer intermediate. The obtained intermediate of the polysiloxane-polyalkylene glycol block copolymer had a content of the structure derived from polysiloxane (A) of 50% by mass, a carboxyl group content of 0.95mmol/g, a number average molecular weight of 14,300 and a weight average molecular weight of 32,000. The results are shown in table 1.

[ Synthesis example 3]

A100 mL 2-neck flask was charged with 10.0g of both-end maleic anhydride-modified silicone oil (X-22-168 AS, manufactured by shin-Etsu chemical Co., Ltd., weight average molecular weight 1300, 5% weight loss temperature 299 ℃ C.), 6.5g of poly-1, 4-butanediol (polytetrahydrofuran 650, weight average molecular weight 1600, 5% weight loss temperature 263 ℃ C., manufactured by Wako pure chemical industries Co., Ltd.), and 66g of toluene, and then nitrogen gas was substituted. Then, it was heated to 120 ℃ to react for 8 hours, to obtain a colorless transparent liquid. After toluene was removed in an evaporator, the residue was dried in a vacuum dryer at 80 ℃ for 18 hours to completely remove toluene. The obtained intermediate polysiloxane-polyalkylene glycol block copolymer was a colorless transparent liquid, and the content of the structure derived from polysiloxane (A) was 61% by mass, the carboxyl group content was 0.68mmol/g, the number average molecular weight was 27,000, and the weight average molecular weight was 49,000. The results are shown in table 1.

[ Synthesis example 4]

A100 mL separable flask was charged with 10.0g of both-end maleic anhydride-modified silicone oil (X-22-168 AS, manufactured by shin-Etsu chemical Co., Ltd., weight-average molecular weight 1300, 5% weight loss temperature 299 ℃ C.) and 10.0g of poly-1, 4-butanediol (polytetrahydrofuran 1,000, weight-average molecular weight 2700, 5% weight loss temperature 275 ℃ C.) to conduct nitrogen substitution. Then, it was heated to 120 ℃ to react for 0.5 hour, to obtain a polysiloxane-polyalkylene glycol block copolymer intermediate. The obtained intermediate of the polysiloxane-polyalkylene glycol block copolymer had a content of a structure derived from polysiloxane (A) of 50% by mass, a carboxyl group content of 1.00mmol/g, a number average molecular weight of 4,400, and a weight average molecular weight of 8,900. The results are shown in table 1.

[ Synthesis example 5]

A100 mL separable flask was charged with 10.0g of amino-modified silicone oil at both ends (KF-8010, weight average molecular weight 1200, 5% weight loss temperature 295 ℃ C., manufactured by shin-Etsu chemical Co., Ltd.) and 10.0g of poly-1, 4-butanediol (polytetrahydrofuran 1,000, weight average molecular weight 2700, 5% weight loss temperature 275 ℃ C., manufactured by Wako pure chemical industries Co., Ltd.), and 3.8g of pyromellitic dianhydride (manufactured by Tokyo chemical industries Co., Ltd.) was added to replace with nitrogen. Then, it was heated to 100 ℃ to react for 8 hours, to obtain a polysiloxane-polyalkylene glycol block copolymer intermediate. The obtained intermediate of the polysiloxane-polyalkylene glycol block copolymer had a content of a structure derived from polysiloxane (A) of 50% by mass, a carboxyl group content of 0.95mmol/g, a number average molecular weight of 12,200, and a weight average molecular weight of 25,000. The results are shown in table 1.

Production example 1

15g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in Synthesis example 1 and 0.85g of triethyl orthoacetate were charged into a 100mL separable flask, and the mixture was purged with nitrogen and heated to 70 ℃ to react for 6 hours. Then, it was dried under vacuum at 80 ℃ for 12 hours to remove by-products, to obtain a polysiloxane-polyalkylene glycol block copolymer. The polysiloxane-polyalkylene glycol block copolymer obtained had a content of the structure derived from polysiloxane (A) of 50 mass%, a carboxyl group content of 0.66mmol/g, a number average molecular weight of 38,600, and a weight average molecular weight of 112,900. The results are shown in table 1.

Production example 2

15g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in Synthesis example 2 and 0.51g of triethyl orthoacetate were charged into a 100mL separable flask, and the mixture was purged with nitrogen and heated to 70 ℃ to react for 6 hours. Then, it was dried under vacuum at 80 ℃ for 12 hours to remove by-products, to obtain a polysiloxane-polyalkylene glycol block copolymer. The polysiloxane-polyalkylene glycol block copolymer obtained had a content of the structure derived from polysiloxane (A) of 50% by mass, a carboxyl group content of 0.74mmol/g, a number average molecular weight of 19,000, and a weight average molecular weight of 50,200. The results are shown in table 1.

Production example 3

15g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in Synthesis example 2 and 0.78g of triethyl orthoacetate were charged in a 100mL separable flask, purged with nitrogen, and heated to 70 ℃ to react for 6 hours. Then, it was dried under vacuum at 80 ℃ for 12 hours to remove by-products, to obtain a polysiloxane-polyalkylene glycol block copolymer. The obtained polysiloxane had a structure derived from polysiloxane (A) content of 50% by mass, a carboxyl group content of 0.63mmol/g, a number average molecular weight of 18,600 and a weight average molecular weight of 47,400. The results are shown in table 1.

Production example 4

15g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in Synthesis example 2 and 1.11g of triethyl orthoacetate were charged into a 100mL separable flask, and the mixture was purged with nitrogen and heated to 70 ℃ to react for 6 hours. Then, the by-products were removed by drying under vacuum at 80 ℃ for 12 hours to obtain a polysiloxane-polyalkylene glycol block copolymer. The polysiloxane-polyalkylene glycol block copolymer obtained had a content of the structure derived from polysiloxane (A) of 49% by mass, a carboxyl group content of 0.49mmol/g, a number average molecular weight of 17,000 and a weight average molecular weight of 41,700. The results are shown in table 1.

Production example 5

15g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in Synthesis example 2 and 1.39g of triethyl orthoacetate were charged into a 100mL separable flask, and the mixture was purged with nitrogen and heated to 70 ℃ to react for 6 hours. Then, it was dried under vacuum at 80 ℃ for 12 hours to remove by-products, to obtain a polysiloxane-polyalkylene glycol block copolymer. The polysiloxane-polyalkylene glycol block copolymer obtained had a content of the structure derived from polysiloxane (A) of 49% by mass, a carboxyl group content of 0.38mmol/g, a number average molecular weight of 17,000 and a weight average molecular weight of 43,300. The results are shown in table 1.

Production example 6

15g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in Synthesis example 2 and 0.72g of trimethyl orthoacetate were charged in a 100mL separable flask, and the mixture was heated to 70 ℃ under nitrogen substitution to react for 6 hours. Then, it was dried under vacuum at 80 ℃ for 12 hours to remove by-products, to obtain a polysiloxane-polyalkylene glycol block copolymer. The polysiloxane-polyalkylene glycol block copolymer obtained had a content of the structure derived from polysiloxane (A) of 50% by mass, a carboxyl group content of 0.55mmol/g, a number average molecular weight of 14,900 and a weight average molecular weight of 37,200. The results are shown in table 1.

Production example 7

Into a 100mL separable flask was charged 15g, 2-ethyl-2-1.00g of oxazoline was purged with nitrogen, and the mixture was heated to 100 ℃ to react for 5 hours, thereby obtaining a polysiloxane-polyalkylene glycol block copolymer. The polysiloxane-polyalkylene glycol block copolymer obtained had a content of the structure derived from polysiloxane (A) of 47 mass%, a carboxyl group content of 0.30mmol/g, a number average molecular weight of 8,800, and a weight average molecular weight of 17,700. The results are shown in table 1.

Production example 8

15g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in Synthesis example 2 and 1.12g of N, N-dimethylformamide dimethyl acetal were put into a 100mL separable flask, and the mixture was heated to 50 ℃ under nitrogen substitution to react for 5 hours. Then, it was dried under vacuum at 80 ℃ for 12 hours to remove by-products, to obtain a polysiloxane-polyalkylene glycol block copolymer. The polysiloxane-polyalkylene glycol block copolymer obtained had a content of the structure derived from polysiloxane (A) of 50% by mass, a carboxyl group content of 0.32mmol/g, a number average molecular weight of 10,500 and a weight average molecular weight of 21,900. The results are shown in table 1.

Production example 9

15g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in Synthesis example 2 and 0.85g of phenyl glycidyl ether were charged in a 100mL separable flask, and the mixture was heated to 120 ℃ under nitrogen substitution to react for 6 hours to obtain a polysiloxane-polyalkylene glycol block copolymer. The polysiloxane-polyalkylene glycol block copolymer obtained had a content of the structure derived from polysiloxane (A) of 50% by mass, a carboxyl group content of 0.73mmol/g, a number average molecular weight of 13,800 and a weight average molecular weight of 39,500. The results are shown in table 1.

Production example 10

15g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in Synthesis example 4 and 1.00g of triethyl orthoacetate were charged into a 100mL separable flask, and the mixture was purged with nitrogen and heated to 50 ℃ to react for 6 hours. Then, it was dried under vacuum at 80 ℃ for 12 hours to remove by-products, to obtain a polysiloxane-polyalkylene glycol block copolymer. The polysiloxane-polyalkylene glycol block copolymer obtained had a content of the structure derived from polysiloxane (A) of 50% by mass, a carboxyl group content of 0.51mmol/g, a number average molecular weight of 4,400, and a weight average molecular weight of 9,000. The results are shown in table 1.

Production example 11

15g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in Synthesis example 5 and 0.85g of triethyl orthoacetate were charged into a 100mL separable flask, and the mixture was purged with nitrogen and heated to 70 ℃ to react for 6 hours. Then, it was dried under vacuum at 80 ℃ for 12 hours to remove by-products, to obtain a polysiloxane-polyalkylene glycol block copolymer. The polysiloxane-polyalkylene glycol block copolymer obtained had a content of the structure derived from polysiloxane (A) of 50% by mass, a carboxyl group content of 0.70mmol/g, a number average molecular weight of 30,500 and a weight average molecular weight of 102,900. The results are shown in table 1.

[ reference example 1]

15g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in Synthesis example 2 and 2.16g of triethyl orthoacetate were charged into a 100mL separable flask, and the mixture was purged with nitrogen and heated to 70 ℃ to react for 6 hours. Then, it was dried under vacuum at 80 ℃ for 12 hours to remove by-products, to obtain a polysiloxane-polyalkylene glycol block copolymer. The polysiloxane-polyalkylene glycol block copolymer obtained had a content of the structure derived from polysiloxane (A) of 49 mass%, a carboxyl group content of 0.06mmol/g, a number average molecular weight of 19,400 and a weight average molecular weight of 54,700. The results are shown in table 1.

[ Table 1]

[ example 1]

9.0g of the polysiloxane-polyalkylene glycol block copolymer obtained in production example 2, 38.25g of a biphenyl type epoxy resin (manufactured by Mitsubishi ケミカル corporation, "JeR" (registered trademark) YX4000H) as an epoxy resin, and 21.75g of a phenol novolac type curing agent (manufactured by Mitsubishi Kabushiki Kaisha, H-1) as a curing agent were weighed out in a 150cc stainless steel beaker, and dissolved in an oven at 120 ℃ to homogenize the mixture. Then, tetraphenyl group as a curing accelerator was added0.3g of tetra-p-tolylborate was simply mixed with a stirring bar, and then mixed 1 time at 2000rpm, 80kPa, 1.5 minutes, 1 time at 2000rpm, 1 time at 1.5 minutes, 1 time at 2000rpm, 50kPa, 1.5 minutes, and 2 times at 2000rpm, 0.2kPa, 1.5 minutes by using a revolution mixer "あわとり Tailang" (manufactured by シンキー), to obtain an uncured epoxy resin composition.

The uncured epoxy resin composition was injected into an aluminum mold provided with a spacer made of "テフロン" (registered trademark) having a thickness of 4mm and a release film, and placed in an oven. The temperature of the oven was set at 80 ℃ and maintained for 5 minutes, and then the temperature was raised at a rate of 1.5 ℃/minute until 175 ℃ to cure the epoxy resin for 4 hours, thereby obtaining an epoxy resin cured product having a thickness of 4 mm.

The obtained cured epoxy resin was cut into a size of 10mm in width and 80mm in length, and the flexural modulus and the strain at break were measured by the above-mentioned methods, and as a result, the flexural modulus was 2.1GPa and the strain at break was 15%. The average domain structure diameter of the polysiloxane in the cured product was 130nm (FIG. 1).

The epoxy resin composition had a viscosity of 0.10 pas at 200 ℃ and a ratio of increase in viscosity to the viscosity of an epoxy resin not containing a block copolymer of 2.5 times, and was good in fluidity. The resulting composition exhibits a low elastic modulus, good dispersibility and excellent flowability. The results are shown in table 2.

[ example 2]

An epoxy resin cured product was obtained in the same manner as in example 1, except that 9.0g of the polysiloxane-polyalkylene glycol block copolymer obtained in production example 3 was replaced with the copolymer. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and the flexural modulus was 1.8GPa and the strain at break was 14%. The average domain structure diameter of the polysiloxane in the cured product was 3100nm (FIG. 2).

The epoxy resin composition had a viscosity of 0.11 pas at 200 ℃ and a ratio of increase in viscosity to the viscosity of an epoxy resin not containing a block copolymer of 2.8 times, and was good in fluidity. The resulting composition exhibits a low elastic modulus, good dispersibility and excellent flowability. The results are shown in table 2.

[ example 3]

An epoxy resin cured product was obtained in the same manner as in example 1, except that 9.0g of the polysiloxane-polyalkylene glycol block copolymer obtained in production example 5 was replaced with the copolymer. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and as a result, the flexural modulus was 1.5GPa and the strain at break was 7.2%. The average domain structure diameter of the polysiloxane in the cured product was 34700 nm.

The epoxy resin composition had a viscosity of 0.08 pas at 200 ℃ and a ratio of increase in viscosity to the viscosity of an epoxy resin not containing a block copolymer of 2.0 times, and was good in fluidity. The resulting composition exhibits a low elastic modulus, good dispersibility and excellent flowability. The results are shown in table 2.

[ example 4]

An epoxy resin cured product was obtained in the same manner as in example 1, except that 9.0g of the polysiloxane-polyalkylene glycol block copolymer obtained in production example 6 was replaced with the copolymer. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and as a result, the flexural modulus was 1.9GPa and the strain at break was 15%. The average domain structure diameter of the polysiloxane in the cured product was 430 nm.

The epoxy resin composition had a viscosity of 0.07 pas at 200 ℃ and a ratio of increase in viscosity to that of an epoxy resin not containing a block copolymer of 1.8 times, and was good in fluidity. The resulting composition exhibits a low elastic modulus, good dispersibility and excellent flowability. The results are shown in table 2.

[ example 5]

An epoxy resin cured product was obtained in the same manner as in example 1, except that 9.0g of the polysiloxane-polyalkylene glycol block copolymer obtained in production example 7 was replaced with the copolymer. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and as a result, the flexural modulus was 2.2GPa and the strain at break was 17%. The average domain structure diameter of the polysiloxane in the cured product was 880 nm.

The epoxy resin composition had a viscosity of 0.08 pas at 200 ℃ and a ratio of increase in viscosity to the viscosity of an epoxy resin not containing a block copolymer of 2.0 times, and was good in fluidity. The resulting composition exhibits a low elastic modulus, good dispersibility and excellent flowability. The results are shown in table 2.

[ example 6]

An epoxy resin cured product was obtained in the same manner as in example 1 except that 4.5g of the polysiloxane-polyalkylene glycol block copolymer obtained in production example 4 and 4.5g of the polysiloxane-polyalkylene glycol block copolymer obtained in production example 7 were used instead of the copolymers. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and as a result, the flexural modulus was 2.1GPa and the strain at break was 15%. The average domain structure diameter of the polysiloxane in the cured product was 2010 nm.

The epoxy resin composition had a viscosity of 0.07 pas at 200 ℃ and a ratio of increase in viscosity to that of an epoxy resin not containing a block copolymer of 1.8 times, and was good in fluidity. The resulting composition exhibits a low elastic modulus, good dispersibility and excellent flowability. The results are shown in table 2.

[ example 7]

An epoxy resin cured product was obtained in the same manner as in example 1, except that 9.0g of the polysiloxane-polyalkylene glycol block copolymer obtained in production example 8 was replaced with the copolymer. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and as a result, the flexural modulus was 1.9GPa and the strain at break was 14%. The average domain structure diameter of the polysiloxane in the cured product was 2050 nm.

The viscosity of the epoxy resin composition at 200 ℃ was 7750 pas, the ratio of increase in viscosity to the viscosity of the epoxy resin not containing the block copolymer was 20 ten thousand times, and the flowability was poor. This is a result of deterioration in fluidity, although the composition exhibits a low elastic modulus and good dispersibility. The results are shown in table 2.

[ example 8]

An epoxy resin cured product was obtained in the same manner as in example 1, except that the copolymer was replaced with the polysiloxane-polyalkylene glycol block copolymer obtained in production example 9. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and as a result, the flexural modulus was 2.1GPa and the strain at break was 11%. The average domain structure diameter of the polysiloxane in the cured product was 180 nm.

The epoxy resin composition had a viscosity of 0.09 pas at 200 ℃ and a ratio of increase in viscosity to the viscosity of an epoxy resin not containing a block copolymer of 2.3 times, and was good in fluidity. The resulting composition exhibits a low elastic modulus, good dispersibility and excellent flowability. The results are shown in table 2.

[ example 9]

An epoxy resin cured product was obtained in the same manner as in example 1, except that the copolymer was replaced with the polysiloxane-polyalkylene glycol block copolymer obtained in production example 10. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and as a result, the flexural modulus was 2.1GPa and the strain at break was 12%. The average domain structure diameter of the polysiloxane in the cured product was 1500 nm.

The epoxy resin composition had a viscosity of 0.06 pas at 200 ℃ and a ratio of increase in viscosity to that of an epoxy resin not containing a block copolymer of 1.5 times, and was good in fluidity. The resulting composition exhibits a low elastic modulus, good dispersibility and excellent flowability. The results are shown in table 2.

[ example 10]

An epoxy resin cured product was obtained in the same manner as in example 1, except that the copolymer was replaced with the polysiloxane-polyalkylene glycol block copolymer obtained in production example 11. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and as a result, the flexural modulus was 2.0GPa and the strain at break was 15%. The average domain structure diameter of the polysiloxane in the cured product was 140 nm.

The epoxy resin composition had a viscosity of 0.12 pas at 200 ℃ and a ratio of increase in viscosity to that of an epoxy resin not containing a block copolymer of 3.0 times, and was good in fluidity. The resulting composition exhibits a low elastic modulus, good dispersibility and excellent flowability. The results are shown in table 2.

Comparative example 1

An epoxy resin cured product was produced in the same manner as in example 1, except that the polysiloxane-polyalkylene glycol block copolymer was not blended. The resulting cured epoxy resin was subjected to a 3-point bending test, and as a result, the flexural modulus was 2.9GPa and the strain at break was 9.5%. The viscosity of the epoxy resin composition at 200 ℃ was 0.04 pas. The results are shown in table 2.

Comparative example 2

An epoxy resin cured product was produced in the same manner as in example 1, except that 9.0g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in synthesis example 1 was used instead of the copolymer. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and as a result, the flexural modulus was 2.5GPa and the strain at break was 11%. The average domain structure diameter of the polysiloxane in the cured product was 53 nm.

The epoxy resin composition had a viscosity of 0.11 pas at 200 ℃ and a ratio of increase in viscosity to the viscosity of an epoxy resin not containing a block copolymer of 2.8 times, and was good in fluidity. The epoxy resin composition exhibits good dispersibility in an epoxy resin cured product and excellent flowability, but has a poor effect of reducing the modulus of elasticity. The results are shown in table 2.

Comparative example 3

An epoxy resin cured product was produced in the same manner as in example 1, except that 9.0g of the intermediate polysiloxane-polyalkylene glycol block copolymer synthesized in synthetic example 2 was used instead of the copolymer. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and as a result, the flexural modulus was 2.3GPa and the strain at break was 10%. The average domain structure diameter of the polysiloxane in the cured product was 51 nm.

The epoxy resin composition had a viscosity of 0.09 pas at 200 ℃ and a ratio of increase in viscosity to the viscosity of an epoxy resin not containing a block copolymer of 2.3 times, and was good in fluidity. The epoxy resin composition exhibits good dispersibility in an epoxy resin cured product and excellent flowability, but has a poor effect of reducing the modulus of elasticity. The results are shown in table 2.

Comparative example 4

An epoxy resin cured product was obtained in the same manner as in example 1, except that 9.0g of the intermediate polysiloxane-polyalkylene glycol block copolymer obtained in synthetic example 3 was replaced with the copolymer. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and as a result, the flexural modulus was 2.4GPa and the strain at break was 11%. The average domain structure diameter of the polysiloxane in the cured product was 65 nm.

The epoxy resin composition had a viscosity of 0.10 pas at 200 ℃ and a ratio of increase in viscosity to the viscosity of an epoxy resin not containing a block copolymer of 2.5 times, and was good in fluidity. The low elastic modulus effect is poor although good dispersibility in an epoxy resin cured product and excellent flowability are exhibited. The results are shown in table 2.

Comparative example 5

An epoxy resin cured product was obtained in the same manner as in example 1, except that 9.0g of the polysiloxane-polyalkylene glycol block copolymer obtained in reference example 1 was replaced with the copolymer. The flexural modulus and the strain at break of the resulting cured epoxy resin were measured, and as a result, the flexural modulus was 1.3GPa and the strain at break was 4.3%. The average domain structure diameter of the polysiloxane in the cured product was 200000 nm.

The epoxy resin composition had a viscosity of 0.12 pas at 200 ℃ and a ratio of increase in viscosity to that of an epoxy resin not containing a block copolymer of 3.0 times, and was good in fluidity. The epoxy resin composition exhibits a low elastic modulus and excellent flowability, but has poor dispersibility in an epoxy resin cured product. The results are shown in table 2.