阅读说明：本技术 涂覆树脂组合物 (Coating resin combination ) 是由 宫内咲奈 丸泽尚 滨田亘人 泽田英夫 于 2018-03-28 设计创作，主要内容包括：本发明旨在提供涂覆树脂组合物,所述涂覆树脂组合物可以形成为具有防雾特性和防污特性的涂覆膜。涂覆树脂组合物用于形成涂覆膜并且包含：含环醚基聚合物(A),所述含环醚基聚合物(A)是可聚合单体组分(a)的聚合物,所述可聚合单体组分(a)包含具有环醚基的烯键式不饱和单体(a11)；和组分(B),所述组分(B)由选自多元羧酸(b1)和多元羧酸酐(b2)中的至少一种化合物组成。所述涂覆树脂组合物的通过在高于或等于100℃且低于或等于所述涂覆树脂组合物的分解温度的温度下加热0.1小时或更长而固化的固化产物的根据JIS R3257的规定所测量的水接触角为90°或更小。(The present invention is intended to provide coating resin combination, the coating resin combination can be formed to have the coating film of anti-fog feature and antifouling properties.Coating resin combination is used to form coating film and includes: based polyalcohol containing cyclic ethers (A), the based polyalcohol containing cyclic ethers (A) is the polymer of polymerizable monomer component (a), and the polymerizable monomer component (a) includes the ethylenically unsaturated monomers (a11) with cyclic ethers base；With component (B), the component (B) selected from least one of polybasic carboxylic acid (b1) and polybasic acid anhydride (b2) compound by forming.The coating resin combination by be greater than or equal to 100 DEG C and less than or equal to the coating resin combination decomposition temperature at a temperature of heating 0.1 hour or longer and cured cured product the water contact angle according to measured by the regulation of JIS R3257 be 90 ° or smaller.)

1. a kind of coating resin combination for being used to form coating film, includes:

Based polyalcohol containing cyclic ethers (A), the based polyalcohol containing cyclic ethers (A) are the polymer of polymerizable monomer component (a), it is described can Polymerizable monomer composition (a) includes the ethylenically unsaturated monomers (a11) with cyclic ethers base；With

Component (B), the component (B) is by being selected from least one of polybasic carboxylic acid (b1) and polybasic acid anhydride (b2) compound group At, wherein

The coating resin combination by being greater than or equal to 100 DEG C and less than or equal to the coating resin combination Heated 0.1 hour at a temperature of decomposition temperature or longer and cured cured product according to measured by the regulation of JIS R3257 Water contact angle be 90 ° or smaller.

2. coating resin combination according to claim 1, wherein

The polymerizable monomer component (a) only includes the monomer (a21) containing 11 or less carbon atoms.

3. coating resin combination according to claim 1, wherein

The polymerizable monomer component (a) is contained with being greater than or equal to 0.5 weight % and being less than or equal to the amount of 60 weight % There are 12 or more monomers (a22).

4. coating resin combination according to claim 3, wherein

The monomer (a22) containing 12 or more includes with (the first selected from least one of the following group Base) acrylate: the alkyl of 8 to 18 carbon atoms and the unbranched alkoxy of 8 to 18 carbon atoms.

5. coating resin combination according to any one of claim 1 to 4, wherein

Relative to polymerizable monomer component (a) described in 100 mass parts, the amount of the ethylenically unsaturated monomers (a11) be greater than or Equal to 40 mass parts and it is less than or equal to 100 mass parts.

6. coating resin combination according to any one of claim 1 to 5, wherein

The weight average molecular weight of the based polyalcohol containing cyclic ethers (A) is greater than or equal to 1000 and is less than or equal to 13000.

7. coating resin combination according to any one of claim 1 to 6, wherein

Relative to carboxyl of 1 equivalent in the component (B), the amount of the cyclic ethers base in the based polyalcohol containing cyclic ethers (A) is greater than Or it is equal to 0.1 equivalent and is less than or equal to 16 equivalents.

8. coating resin combination according to any one of claim 1 to 7, wherein

The based polyalcohol containing cyclic ethers (A) has epoxy group.

9. coating resin combination according to any one of claim 1 to 8, wherein

The based polyalcohol containing cyclic ethers (A) does not have aromatic ring.

10. coating resin combination according to any one of claim 1 to 9, wherein

The component (B) is liquid at 25 DEG C.

11. coating resin combination according to any one of claim 1 to 10, wherein

The component (B) includes at least one of 4- methylhexahydrophthalic anhydride and hexahydrophthalic anhydride.

12. coating resin combination according to any one of claim 1 to 11, wherein

The coating resin combination does not include curing catalysts.

13. coating resin combination according to any one of claim 1 to 12, also includes:

The compound indicated by following formula (1) and at least one of the compound indicated by following formula (2), wherein

In formula (1), R_FIndicate C_aF_2a+1O_b, a indicate be greater than or equal to 1 and be less than or equal to 15 number, b expression be greater than or equal to 0 and be less than or equal to 10 number, R indicates that organic group and n indicate natural number；And

In formula (2), R_FIndicate C_aF_2a+1, number of a expression more than or equal to 1 and less than or equal to 15, x and y indicate that natural number makes X:y is obtained in the range of 1:99 to 60:40,

R_F-(CH₂CH (C (=O) R))_n-R_F···(1)

[chemical formula 1]

14. coating resin combination according to any one of claim 1 to 13, wherein

The coating resin combination is used to form the coating film with anti-fog feature and antifouling properties.

Technical field

The present invention relates to coating resin combinations, and are particularly used for forming the coating resin combination of coating film.

Background technique

A kind of antifog coating agent is disclosed in patent document 1, it includes: the polymerizable unsaturated monomer conduct with carboxyl The polymer of repetitive unit；The crosslinking agent that the simultaneously functional group of covalent bonding can be reacted with carboxyl at least two；Alkali metal Hydroxide；And solvent.

According to patent document 1, antifog coating agent has improved anti-fog feature；However, not considering antifouling properties.

Reference listing

Patent document

Patent document 1:JP 2015-137342 A

Summary of the invention

The present invention is intended to provide coating resin combination, the coating resin combination can be formed to have anti-fog feature With the coating film of antifouling properties.

The coating resin combination of an embodiment according to the present invention is the coated with resins group for being used to form coating film Close object and include: based polyalcohol containing cyclic ethers (A) is the polymer of polymerizable monomer component (a), the polymerisable monomer group Dividing (a) includes the ethylenically unsaturated monomers (a11) with cyclic ethers base；It is polybasic carboxylic acid (b1) and more by being selected from component (B) At least one of first carboxylic acid anhydrides (b2) compound composition and the coating resin combination by being greater than or equal to 100 DEG C and less than or equal to the coating resin combination decomposition temperature at a temperature of heat 0.1 hour or longer and solidify Cured product the water contact angle according to measured by the regulation of JIS R3257 be 90 ° or smaller.

Specific embodiment

One embodiment of the invention is described.

Coating resin combination according to the present embodiment is the group for being used to form the coating film that can cover various substrates Close object.Coating resin combination includes based polyalcohol containing cyclic ethers (A) and component (B).Based polyalcohol containing cyclic ethers (A) is polymerizable list The polymer of body component (a) and include cyclic ethers base, the polymerizable monomer component (a) include the ethylenic bond with cyclic ethers base not It is saturated monomer (a11).Component (B) is by being selected from least one of polybasic carboxylic acid (b1) and polybasic acid anhydride (b2) compound group At.In addition, coating resin combination by being greater than or equal to 100 DEG C and less than or equal to the coating resin combination Heated 0.1 hour at a temperature of decomposition temperature or longer and cured cured product according to measured by the regulation of JIS R3257 Water contact angle be 90 ° or smaller.

When based polyalcohol containing cyclic ethers (A) reacts in coating resin combination with component (B), coating resin combination is solid Change.Therefore, coating resin combination can be formed as coating film.Coating film can have high intensity.In addition, coating film includes logical Cross the hydroxyl for reacting and generating between cyclic ethers base and carboxyl or between cyclic ethers base and anhydrous carboxyl.In addition, coating film can be with Unreacted carboxyl groups comprising the carboxyl or anhydrous carboxyl that are originated from component (B).Think compared with based polyalcohol containing cyclic ethers (A), group (B) is divided to tend to easily move around in coating resin combination, and therefore carboxyl tends to along the surface of coating film appearance It changes places arrangement.Think due to above, coating film can have high-hydrophilic and high oleophobic property, and causing water contact angle is 90 ° Or it is smaller.Therefore, coating film can have high-intensitive, high anti-fog feature and high antifouling properties.In addition, coating film can have pair The high adherence of inorganic oxide (such as glass).Think to realize to the high adherence of inorganic oxide be because are as follows: when making to coat When solidifying on glass, the hydroxyl in inorganic oxide surface tends to contain ring with coating resin combination resin combination The carboxyl or anhydrous carboxyl of component (B) in the cyclic ethers base and coating resin combination of ether based polymer (A) easily react simultaneously Bonding.

Each component in coating resin combination is further described.

As described above, based polyalcohol containing cyclic ethers (A) is the polymer of polymerizable monomer component (a), the polymerisable monomer Component (a) includes the ethylenically unsaturated monomers (a11) with cyclic ethers base.Polymerizable monomer component (a) can only include ethylene linkage Formula unsaturated monomer (a11).Polymerizable monomer component (a) may include ethylenically unsaturated monomers (a11) and not have cyclic ethers The ethylenically unsaturated monomers (a12) of base.

The cyclic ethers base of based polyalcohol containing cyclic ethers (A) includes such as at least one of epoxy group and oxetanyl.It changes Yan Zhi, the cyclic ethers base of ethylenically unsaturated monomers (a11) include such as at least one of epoxy group and oxetanyl.

Relative to 100 mass parts polymerizable monomer components (a), the amount of ethylenically unsaturated monomers (a11) preferably greater than or Equal to 40 mass parts and it is less than or equal to 100 mass parts.When the amount of ethylenically unsaturated monomers (a11) is greater than or equal to 40 mass When part, coating film can have the extra high adhesiveness to inorganic oxide (such as glass).Ethylenically unsaturated monomers (a11) amount is especially preferred greater than or equal to 40 mass parts and is less than or equal to 80 mass parts.In this case, coating film can With good alkali resistance and good acid resistance.Think the high adherence to inorganic oxide, good alkali resistance and good It is good acid proof the reason is as follows that.When the amount of ethylenically unsaturated monomers (a11) is less than or equal to 80 mass parts, in coating film Hydroxyl amount keep it is sufficiently low.Meanwhile when the amount of ethylenically unsaturated monomers (a11) is greater than or equal to 40 mass parts, apply Crosslink density in overlay film sufficiently increases.Therefore, the crosslinking that can be balanced well in the hydrophily and coating film of coating film is close Degree.

Polymerizable monomer component (a) may include the monomer (a21) containing 11 or less carbon atoms.Work as polymerisable monomer When component (a) only includes monomer (a21) containing 11 or less carbon atoms, it can obtain with particularly preferred anti-fog feature Coating film.The reason of thinking particularly preferred anti-fog feature is as follows.Carbon atom number in monomer to hydrophilic functional groups (such as: pass through The hydroxyl for reacting and generating between based polyalcohol containing cyclic ethers (A) and component (B)；With the carboxyl for being originated from component (B)) in coating film Distribution on surface has an impact.In other words, it is believed that when polymerizable monomer component (a) only includes containing 11 or less carbon atoms When monomer (a21), hydrophilic functional groups are well distributed on the surface of coating film, and thus coating film surface obtain it is good Hydrophily.

Polymerizable monomer component (a) can wrap content more than or equal to 0.5 weight % and less than or equal to 60 weight %'s Contain 12 or more monomers (a22).In other words, polymerizable monomer component (a) may include containing 11 or more The monomer (a21) of carbon atom and the monomer (a22) containing 12 or more less, relative to polymerizable monomer component (a) Total amount, the amount of monomer (a21) can be greater than or equal to 40 weight % and be less than or equal to 99.5 weight %；Relative to polymerizable The total amount of monomer component (a), the amount of monomer (a22) can be greater than or equal to 0.5 weight % and be less than or equal to 60 weight %.In In this case, the coating film with particularly preferred antifouling properties can be obtained.The reason of thinking particularly preferred antifouling properties is such as Under.When the amount of monomer (a22) is greater than or equal to 0.5 weight %, there is the strand with hydrophilic functional groups in coating film The space moderately to move around causes the small interaction between the surface of coating film and oil droplet, and the thus table of coating film Face obtains high oleophobic property.In addition, when the amount of monomer (a22) is less than or equal to 60 weight %, the molecule with hydrophilic functional groups Chain tends not on the surface of coating film excessively intensively, and the movement of strand tends not to be prevented from.

In addition, monomer (a22) preferably includes the monomer (a221) containing 12 or more and 22 or less carbon atoms, and And the total amount relative to polymerizable monomer component (a), the amount of monomer (a221) be preferably greater than or equal to 0.5 weight % and be less than or Equal to 30 weight %.In addition, monomer (a22) is it is preferably not included that contain the monomer more than 22 carbon atoms.In this case, it applies Overlay film can have extra high antifouling properties.Think to realize extra high antifouling properties be because are as follows: containing being more than 22 carbon originals The amount of the monomer of son is low, to prevent the strand in coating film surface from becoming oleophylic.

Monomer (a22) is preferably included with (methyl) acrylate selected from least one of the following group: 8 to 18 The unbranched alkoxy of the alkyl of carbon atom and 8 to 18 carbon atoms.In this case, coating film can have extra high anti- Dirty characteristic.The reason of thinking extra high antifouling properties is as follows.Alkyl or unbranched alkoxy from (methyl) acrylate are suitable Locality adjusts the density of the hydrophilic functional groups (such as carboxyl) in coating film surface, causes mutual between hydrophilic radical and dirt Declines, thus dirt tends not to be attached to coating film.In addition, coating film can be with when carbon atom number is 12 or less Keep good hardness.The reason of thinking good hardness is as follows.When the alkyl or straight chain alcoxyl for being originated from (methyl) acrylate When carbon atom number in base is become more than 12, strand becomes oleophylic and is exposed to the surface of coating film, thus the table of coating film Face shows plasticity.Relative to the amount of polymerizable monomer component (a), the amount of (methyl) acrylate is preferably greater than or equal to 0.5 weight % and be less than or equal to 30 weight %.

It will include that monomer in polymerizable monomer component (a) is defined as above-mentioned tool note that according to whether comprising cyclic ethers base No matter there are the ethylenically unsaturated monomers (a11) or the above-mentioned ethylenically unsaturated monomers (a12) without cyclic ethers base of cyclic ethers base Carbon atom number is how many.In addition, according to carbon atom number, will include monomer in polymerizable monomer component (a) be defined as containing The monomer (a21) of 11 or less carbon atoms containing 12 or more monomers (a22) or contains 12 or more More and 22 or less carbon atoms monomer (a221), regardless of whether including cyclic ethers base.Therefore, such monomer, example may be present As it is not only defined as ethylenically unsaturated monomers (a11) but also is defined as the monomer containing 11 or less carbon atoms (a21)。

Based polyalcohol containing cyclic ethers (A) does not preferably have aromatic ring.In other words, polymerizable monomer component (a) does not preferably have virtue Ring.In this case, coating film can have the high grade of transparency.Furthermore, it is possible to prevent the xanthochromia of coating film when irradiated with light. In other words, coating film can have high-light-fastness and high yellowing resistance.

Not only it is defined as monomer (a11) but also is defined as the monomer of monomer (a21) (that is, there is cyclic ethers base and contain Have the monomer of 11 or less carbon atoms) example include glycidyl methacrylate (carbon atom number 7), acrylic acid 3, 4- epoxycyclohexanecarboxylate (carbon atom number 10), 3- ethyl -3- methacryloxymethyl oxetanes (carbon atom number For 10), (carbon atom number is for 4- hydroxybutyl acrylate glycidol ether and methacrylic acid 3,4- epoxycyclohexanecarboxylate 11)。

Not only be defined as monomer (a12) and also be defined as monomer (a21) monomer (that is, do not have cyclic ethers base and Monomer containing 11 or less carbon atoms) example include methyl methacrylate (carbon atom number 5), tert-butyl acrylate (carbon atom number 7), Tert-butyl Methacrylate (carbon atom number 8) and benzyl methacrylate (carbon atom number 11).

Not only be defined as monomer (a12) and also be defined as monomer (a22) monomer (that is, do not have cyclic ethers base and Monomer containing 12 or more) example include the different nonyl ester (carbon atom number 12) of acrylic acid, methacrylic acid 2- (carbon atom number is for the different nonyl ester (carbon atom number 13) of ethylhexyl (carbon atom number 12), methacrylic acid, isodecyl acrylate 13), isodecyl methacrylate (carbon atom number 14), the positive lauryl of acrylic acid (carbon atom number 15), methacrylic acid be just (carbon atom number is for lauryl (carbon atom number 16), the different octadecyl ester of acrylic acid (carbon atom number 21), n-stearyla crylate 21), the different octadecyl ester of methacrylic acid (carbon atom number 22) and the positive octadecyl ester of methacrylic acid (carbon atom number 22).

Illustrate the synthesis of based polyalcohol containing cyclic ethers (A).Based polyalcohol containing cyclic ethers (A) can be by making polymerizable monomer component (a) polymerization is to synthesize.Known polymerization can be used.For example, when synthesizing based polyalcohol containing cyclic ethers by solution polymerization process It (A), can be molten by heating the reaction comprising polymerizable monomer component (a), polymerization initiator and solvent under an inert atmosphere when Liquid come make polymerizable monomer component (a) polymerize, it is possible thereby to synthesize based polyalcohol containing cyclic ethers (A).

The example of solvent used in solution polymerization process includes: water；The alcohol of linear chain or branched chain, two pure and mild polyalcohols, such as Methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, hexanol and ethylene glycol；Ketone, such as acetone, methyl ethyl ketone, hexamethylene；Aromatic hydrocarbons Class, such as toluene and dimethylbenzene；Petroleum aromatic mixed solvent, such as Swazol series is (by Maruzen Petrochemical Co., Ltd is produced) and SOLVESSO series (being produced by Exxon Chemical Corporation)；Dioxane, for example, it is molten Fine agent and butyl cellosolve；Carbitol class, such as carbitol, butyl carbitol, diethylene glycol monomethyl ether acetic acid esters；Propylene glycol alkane Base ethers, such as propylene glycol monomethyl ether；Polypropylene glycol alkyl ether class, such as dipropylene glycol methyl ether；Acetate esters, such as acetic acid second Ester, butyl acetate and cellosolve acetate；TwoAlkane；Dimethylformamide；With dialkyl group glycol ethers.Chemical combination listed above Object can be used as solvent alone or in combination.

The example of polymerization initiator includes: peroxide, such as ammonium persulfate, benzoyl peroxide and peroxidating laurel Acyl；And azo-compound, such as 2,2'- azodiisobutyronitrile, 2,2'- azo, two -2- methylbutyronitrile, 2,2'- azo two -2, 4- methyl pentane nitrile, two -1- cyclohexane nitrile of 1,1'- azo, two -4- cyanopentanoic acid of 4,4'- azo and 2,2'- azo two-(2- amidine Base propane)-dihydrochloride.

For the purpose for the molecular weight for for example adjusting based polyalcohol containing cyclic ethers (A), if it is necessary, can be into reaction solution Add chain-transferring agent.The example of chain-transferring agent includes: compound with mercapto, such as lauryl mercaptan, lauryl mercaptan And thioglycerin；α-methylstyrene dimer, such as 2,4- diphenyl -4-methyl-1-pentene；And inorganic salts, such as sodium hypophosphite And sodium hydrogensulfite.The amount for suitably determining chain-transferring agent, so that the weight average molecular weight of based polyalcohol containing cyclic ethers (A) is in centainly In range.

The weight average molecular weight of based polyalcohol containing cyclic ethers (A) is preferably lower than or equal to 100000.Based polyalcohol containing cyclic ethers (A) Weight average molecular weight is more preferably equal to or greater than 1000 and is less than or equal to 13000.In this case, coating film can have spy Not good characteristic and the extra high adhesiveness to the substrate made of inorganic oxide (such as glass).Note that Weight-average molecular Amount is the polystyrene conversion value measured by gel permeation chromatography.

The equivalent of cyclic ethers base in based polyalcohol containing cyclic ethers (A) is preferably greater than or equal to 140 and is less than or equal to 400.In In this case, based polyalcohol containing cyclic ethers (A) can have good reactivity, and coating film can have good hardness With good hydrophily.Specifically, when the equivalent of cyclic ethers base is less than or equal to 400, coating film can have high crosslink density. Therefore, coating film can have particularly preferred adhesiveness, particularly preferred hardness, particularly preferred water resistance and particularly preferred chemically-resistant Property.In addition, when the equivalent of cyclic ethers base is greater than or equal to 140, it is therefore prevented that the amount of the hydroxyl in coating film is excessively increased.Therefore, Coating film can have particularly preferred water resistance and particularly preferred chemical resistance.

Illustrate component (B).As described above, component (B) is by being selected from polybasic carboxylic acid (b1) and polybasic acid anhydride (b2) extremely A kind of few compound composition.

Component (B) is liquid preferably at 25 DEG C.In this case, coating film can have high homogeneity and especially High hydrophily.Think to realize high homogeneity and extra high hydrophily be because are as follows: when component (B) is liquid, component (B) It is well distributed in the composition, causes by reacting the hydroxyl generated between based polyalcohol containing cyclic ethers (A) and component (B) It is well distributed in coating film.

Component (B) does not preferably include aromatic group.In this case, coating film can have the high grade of transparency.In addition, can To prevent the xanthochromia of coating film when irradiated with light.In other words, coating film can have high-weatherability and high yellowing resistance.

In the case where component (B) includes polybasic carboxylic acid (b1), polybasic carboxylic acid (b1) particularly preferably includes 4- methyl hexahydro At least one of phthalic acid and hexahydrophthalic acid.It is more in the case where component (B) includes polybasic acid anhydride (b2) First carboxylic acid anhydrides (b2) particularly preferably includes at least one of 4- methylhexahydrophthalic anhydride and hexahydrophthalic anhydride. In these cases, coating film can have extra high homogeneity and extra high hydrophily.

Relative to carboxyl of 1 equivalent in component (B), the amount of the cyclic ethers base in based polyalcohol containing cyclic ethers (A) is preferably greater than Or it is equal to 0.1 equivalent and is less than or equal to 16 equivalents.In this case, coating film can have extra high hydrophily.Recognize For realize extra high hydrophily be because are as follows: unreacted carboxyl is well distributed on the surface of coating film in component (B).This Outside, when the amount of cyclic ethers base is greater than or equal to 0.1 equivalent, it is therefore prevented that unreacted carboxyl is present in excess in the surface of coating film On, and therefore can keep the adhesiveness and water resistance of coating film.Furthermore, it is therefore prevented that a part of component (B) is still in coating film Surface on unreacted, cause to prevent the uneven of the coating film as caused by the volatilization of this part of component (B) when heated. In addition, the high crosslink density of coating film can be kept when the amount of cyclic ethers base is less than or equal to 16 equivalent, and therefore keep coating Good hardness, good adhesive property and the excellent in chemical resistance of film.The amount of cyclic ethers base is more preferably equal to or greater than 0.3 equivalent.Cyclic ethers The amount of base is more preferably less than or equal to 5 equivalents.

Coating resin combination may include curing catalysts (also referred to as curing accelerator).Curing catalysts be make include The compound accelerated is reacted between the compound of cyclic ethers base and the carboxylic compound of packet.Known solidification catalysis can be used Agent.The example of curing catalysts includes imidazolium compounds, organic phosphorus compound, tertiary amine and quaternary ammonium salt.However, coated with resins combines Object does not preferably include curing catalysts.Even if coating resin combination does not include curing catalysts, in coating resin combination Reacting between based polyalcohol containing cyclic ethers (A) and component (B) can also successfully carry out.In addition, coating resin combination not In the case where curing catalysts, the purposes of coating film is not restricted because of curing catalysts, and coating film can be used for Such as food hygiene.

Coating resin combination, which may include, contains fluorinated alkyl compound (C1) (hereinafter, also referred to as by what following formula (1) indicated Contain in fluorinated alkyl compound (C2) (hereinafter, also referred to as compound (C2)) for compound (C1)) and by what following formula (2) indicated At least one.Compound (C1) and compound (C2) can further improve the hydrophily and oleophobic property of coating film.

In formula (1), R_FRespectively indicate C_aF_2a+1O_b, number of a expression more than or equal to 1 and less than or equal to 15, b expression Number more than or equal to 0 and less than or equal to 10, R indicate that organic group and n indicate natural number.In formula (2), R_FIt indicates C_aF_2a+1, number of a expression more than or equal to 1 and less than or equal to 15.In formula (2), x and y indicate that natural number makes x:y 1: In the range of 99 to 60:40.

R_F-(CH₂CH (C (=O) R))_n-R_F…(1)

[chemical formula 1]

Further illustrate (C1) containing fluorinated alkyl compound.

Organic group R in formula (1) are as follows: for example, hydroxyl；Linear or branched alkyl group ether, such as methyl ether, ethylether Base, propyl ether and isopropyl ether；Secondary amino group, such as morpholino base, (1,1- dimethyl -3- oxo isobutyl group) amino and two Methylamino；Or tertiary amino.

In formula (1), n expression is greater than or the number equal to 1 and less than or equal to 450.

Compound (C1) is preferably oligomer, and particularly, and the number-average molecular weight of compound (C1) is preferably greater than or waits In 500 and be less than or equal to 30000.Number-average molecular weight is more preferably equal to or greater than 1000 and less than or equal to 15000, and into One step is preferably greater than or equal to 2000 and is less than or equal to 8000.Number-average molecular weight is measured by gel permeation chromatography.

Compound (C1) includes being selected from least one of the following compound: for example, having dimethylacrylamide residue As (CH₂CH (C (=O) R)) the oligomer of dimethylacrylamide containing fluoro-alkyl, have N- (1,1- dimethyl -3- oxo Butyl) acrylamide residue conduct (CH₂CH (C (=O) R)) N- containing fluoro-alkyl (1,1- dimethyl -3- oxo butyl) third Acrylamide oligomer and have acryloyl morpholine residue be used as (CH₂CH (C (=O) R)) acryloyl morpholine containing fluoro-alkyl Oligomer.

Illustrate compound (C2).

Formula (2) is to indicate to constitute each structural unit in the structure and compound (C2) of the structural unit of compound (C2) The nominal composition of ratio.In other words, compound (C2) is the structure list that the left side for being included in formula (2) with the molar ratio of x:y indicates The member acrylate monomer residue of fluoro-alkyl (that is, with) and the structural unit indicated on the right side of formula (2) are (that is, acrylic acid Residue) copolymer.Compound (C2) can also be limited to by making the acrylate monomer with fluoro-alkyl and propylene The copolymer that acid is obtained with the molar ratio copolymerization of x:y.

Acrylate monomer with fluoro-alkyl has such as CH₂CHCOOCH₂CH₂R_FStructure.With fluoro-alkyl Acrylate monomer include such as fluoroalkyl base ethyl ester.Acrylate monomer with fluoro-alkyl particularly preferably wraps Include selected from least one of the following compound: acrylic acid 2- (perfluoro butyl) ethyl ester, acrylic acid 2- (perfluoro hexyl) ethyl ester and Acrylic acid 2- (perfluoro capryl) ethyl ester.

In formula (2), R_FIn a be especially preferred greater than or equal to 4 and be less than or equal to 8.In addition, in formula (2), x:y Particularly preferably in the range of 3:97 to 40:60.

The number-average molecular weight of compound (C2) is preferably greater than or equal to 500 and is less than or equal to 10000, and more preferably big In or be equal to 1500 and be less than or equal to 5000.Number-average molecular weight is measured by gel permeation chromatography.

Compound (C2) can be for example, by making acrylic acid by polymerization appropriate and with the propylene of fluoro-alkyl Acid ester monomer is copolymerized to synthesize.The example of polymerization includes known polymerization, such as wherein molten using the routine of solvent Liquid polymerization.

Think since there are fluoro-alkyl chain, compound (C1) and compounds (C2) to improve in particular coating in molecule The hydrophily and oleophobic property of film.

Coating resin combination particularly preferably includes compound (C1).Compound (C1) is particularly helpful to improve coating film Hydrophily and oleophobic property, and improve the anti-fog feature of coating film.Think the improvement of realization hydrophily, oleophobic property and anti-fog feature It is that there is in its molecular skeleton perfluoroalkyl or perfluor oxa- with polar group and at its end because of are as follows: compound (C1) Alkyl.

When coating resin combination includes at least one of compound (C1) and compound (C2), relative to containing cyclic ethers The total amount of based polyalcohol (A) and component (B), the total amount of compound (C1) and compound (C2) is preferably big in coating resin combination In or equal to 1 weight % and it is less than or equal to 50 weight %.When the total amount of compound (C1) and compound (C2) is greater than or equal to 1 When weight %, coating film can have particularly preferred anti-fog feature and particularly preferred antifouling properties.When compound (C1) and chemical combination When the total amount of object (C2) is less than or equal to 50 weight %, coating resin combination can be made to solidify well.Compound (C1) and The total amount of compound (C2) is more preferably equal to or greater than 5 weight % and more preferably less than or equal to 10 weight %.

If it is necessary, coating resin combination may include solvent.The example of solvent contains with being synthesized by solution polymerization process The examples detailed above of solvent used in cyclic ethers based polyalcohol (A) is identical.

Coating resin combination can be applied in substrate and then be heated, so that based polyalcohol containing cyclic ethers (A) and component (B) it reacts, it is possible thereby to solidify coating resin combination.Therefore, coating film can be formed by coating resin combination.As above Described, coating film can have high-hydrophilic and high oleophobic property.Therefore, coating film can be provided good anti-with based surface Mist characteristic and good antifouling properties.There is no limit for the material and shape of substrate.As described above, when substrate is by inorganic oxide When (such as glass) is made, coating film can have the extra high adhesiveness to substrate.

The thickness of coating film is preferably greater than or equal to 1 μm.When thickness is greater than or equal to 1 μm, coating film be can have pair The good adhesive property of substrate (such as glass).Think realize good adhesive property be because are as follows: when thickness be greater than or equal to 1 μm when, apply Overlay film can have appropriate durability.

As described above, coating film can have high-hydrophilic and can have 120 ° or smaller water contact angle.As above Described, water contact angle is obtained and solidifying coating resin combination by using the method measurement of JIS R3257 defined The water contact angle of cured product determine.In order to make coating film that there is high-hydrophilic, the water contact of coating film or cured product Angle is preferably 90 ° or smaller.Water contact angle is preferably 40 ° or bigger.In this case, coating film can have excellent anti- Mist characteristic.Think to realize excellent anti-fog feature be because are as follows: the hydrophily and oleophobic property of cured product or coating film obtain very well Ground balance.Water contact angle is more preferably 60 ° or bigger.

In addition, coating film can have high oleophobic property as described above, and therefore coating film can have 10 ° or bigger Dodecane contact angle.Dodecane contact angle is measured by using the method for JIS R3257 defined by making coated with resins group Object is closed to solidify and the dodecane contact angle of cured product that obtains determines.In order to make coating film that there is high oleophobic property, coating film Or the dodecane contact angle of cured product is preferably 15 ° or bigger.In this case, coating film or cured product can have Good oleophobic property generates the especially excellent antifouling properties of coating film or cured product.Dodecane contact angle is more preferably 20 ° Or it is bigger.

Since based polyalcohol containing cyclic ethers (A) is sufficiently reacted with component (B), in addition to high-hydrophilic and high oleophobic property, Coating film can also have high rigidity.Therefore, the pencil hardness of coating film can be for B or harder.

In addition, as described above, coating film has the high adherence to glass.For example, when to being formed on flat glass substrate Coating film carry out JIS K5600 5-6 in defined using glassine paper adhesive tape disbonded test when, the edge of cutting line Be it is smooth, do not observe the removing of coating film in the infall of cutting line, and 10 × 10 squares that cutting line is surrounded Part is not peeled off.

These characteristics of coating film can be realized by adjusting the composition of coating resin combination within the above range.

The coating film with anti-fog feature and antifouling properties can be obtained by coating resin combination.As described above, realizing Anti-fog feature and antifouling properties are because are as follows: coating film has high-hydrophilic and high oleophobic property.