阅读说明：本技术 不饱和聚酯树脂组合物、成型材料、成型品、及电动车辆的电池组壳体 (Unsaturated polyester resin composition, molding material, molded article, and battery pack case for electric vehicle ) 是由 赤井郁雄 箱谷昌宏 冢本贵史 于 2019-10-16 设计创作，主要内容包括：不饱和聚酯树脂组合物包含树脂成分、氢氧化铝和阻燃剂,所述树脂成分包含不饱和聚酯、聚合性单体及低收缩剂。不饱和聚酯为多元酸与多元醇的聚合产物,所述多元酸包含规定比例的具有烯键式不饱和双键的多元酸。作为低收缩剂的聚乙酸乙烯酯相对于树脂成分而言为规定比例。氢氧化铝相对于树脂成分而言为规定比例。(The unsaturated polyester resin composition comprises a resin component, aluminum hydroxide and a flame retardant, wherein the resin component comprises an unsaturated polyester, a polymerizable monomer and a low shrinkage agent. The unsaturated polyester is a polymerization product of a polybasic acid containing a prescribed proportion of a polybasic acid having an ethylenically unsaturated double bond and a polyhydric alcohol. The polyvinyl acetate as the low shrinkage agent is in a predetermined ratio with respect to the resin component. The ratio of aluminum hydroxide to the resin component is specified.)

1. An unsaturated polyester resin composition comprising a resin component, aluminum hydroxide and a flame retardant, wherein the resin component comprises an unsaturated polyester, a polymerizable monomer and a low shrinkage agent,

the unsaturated polyester is a polymerization product of polybasic acid and polyalcohol,

the polybasic acid comprises a polybasic acid having an ethylenically unsaturated double bond,

the proportion of the polybasic acid having an ethylenically unsaturated double bond is 80 mol% or more based on 100 mol% of the polybasic acid,

the low profile agent comprises a polyvinyl acetate,

the mixing ratio of the polyvinyl acetate is 3 to 10 parts by mass with respect to 100 parts by mass of the resin component,

the amount of the aluminum hydroxide is 50 parts by mass or more and less than 150 parts by mass per 100 parts by mass of the resin component.

2. The unsaturated polyester resin composition according to claim 1, wherein the blending ratio of the flame retardant is 15 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the aluminum hydroxide.

3. The unsaturated polyester resin composition according to claim 1, wherein the flame retardant is a phosphorus-based flame retardant.

4. A molding material comprising the unsaturated polyester resin composition according to claim 1 and a reinforcing fiber,

the total amount of the components other than the aluminum hydroxide and, if necessary, the filler other than the filler in the unsaturated polyester resin composition is 40 to 70 vol%.

5. A molded article comprising a cured product of the molding material according to claim 4.

6. The molded article according to claim 5, wherein the linear expansion coefficient is 20ppm/° C or more and 25ppm/° C or less.

7. The molded article of claim 5, wherein a battery pack case for an electric vehicle.

8. A battery pack case for an electric vehicle, characterized by comprising an aluminum member and the molded article according to claim 5 integrally.

Technical Field

The present invention relates to an unsaturated polyester resin composition, a molding material, a molded article, and a battery pack case for an electric vehicle, and more particularly, to an unsaturated polyester resin composition, a molding material containing an unsaturated polyester resin composition, a molded article containing a cured product of a molding material, and a battery pack case for an electric vehicle including a cured product of a molding material.

Background

Conventionally, a molded article formed of a molding material (particularly SMC (sheet molding compound)) containing an unsaturated polyester resin has been replacing a part of a steel sheet of an automobile because of its excellent appearance, mechanical properties, water resistance, corrosion resistance, and the like.

As such a molding material, for example, a molding material containing an unsaturated polyester resin, a low shrinkage agent, calcium carbonate as a filler, and carbon fibers as reinforcing fibers is proposed (for example, see patent document 1 listed below).

More specifically, molded articles formed from such molding materials are mainly used in combination with steel sheets at locations where rigidity and heat resistance are required, such as trunk lids, engine covers, and engine oil pans and rocker covers.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2009-209269

Disclosure of Invention

Problems to be solved by the invention

In recent years, from the viewpoint of weight reduction, such molded articles are strongly desired to be used in combination with light metals in addition to steel sheets.

However, the molded article formed from the molding material of patent document 1 has a smaller linear expansion coefficient than that of light metal. Therefore, when the molded article is combined with a light metal, there is a problem that dimensional stability is lowered due to a difference between the linear expansion coefficient of the molded article and the linear expansion coefficient of the light metal.

In particular, if a molded article is integrally molded with a light metal, the influence of the above-described difference becomes more significant, and there is a problem that dimensional stability is further lowered.

Further, such molded articles are sometimes required to have low shrinkage for reducing warpage and deformation and flame retardancy for delaying the spread of fire during vehicle fire.

The purpose of the present invention is to provide an unsaturated polyester resin composition for obtaining a molded article that has excellent flame retardancy and low shrinkage, and is excellent in dimensional stability even when combined with a light metal member, a molding material comprising the unsaturated polyester resin composition, a molded article comprising a cured product of the molding material, and a battery pack case for an electric vehicle that is provided with a cured product of the molding material.

Means for solving the problems

The present invention [1] is an unsaturated polyester resin composition comprising a resin component, aluminum hydroxide, and a flame retardant, wherein the resin component comprises an unsaturated polyester, a polymerizable monomer, and a low shrinkage agent, the unsaturated polyester is a polymerization product of a polybasic acid and a polyhydric alcohol, the polybasic acid comprises a polybasic acid having an ethylenically unsaturated double bond, the blending ratio of the polybasic acid having an ethylenically unsaturated double bond is 80 mol% or more with respect to 100 mol% of the polybasic acid, the low shrinkage agent comprises polyvinyl acetate, the blending ratio of the polyvinyl acetate is 3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin component, and the blending ratio of the aluminum hydroxide is 50 parts by mass or more and less than 150 parts by mass with respect to 100 parts by mass of the resin component.

The invention [2] comprises the unsaturated polyester resin composition according to [1], wherein the blending ratio of the flame retardant is 15 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the aluminum hydroxide.

The invention [3] comprises the unsaturated polyester resin composition according to [1] or [2], wherein the flame retardant is a phosphorus flame retardant.

The invention [4] comprises a molding material comprising the unsaturated polyester resin composition according to [1] to [3] and a reinforcing fiber, wherein the total amount of components other than the aluminum hydroxide and, if necessary, a filler other than the filler in the unsaturated polyester resin composition is 40 to 70 vol%.

The invention [5] comprises a molded article comprising a cured product of the molding material according to [4 ].

The invention [6] is the molded article according to [5], which has a linear expansion coefficient of not less than 20 ppm/DEG C and not more than 25 ppm/DEG C.

The invention [7] includes the molded article according to the above [5] or [6], which is used for a battery pack case of an electric vehicle.

The invention [8] includes a battery pack case for an electric vehicle, which integrally includes an aluminum member and the molded article according to any one of the above [5] to [7 ].

ADVANTAGEOUS EFFECTS OF INVENTION

In the unsaturated polyester resin composition of the present invention, the polybasic acid of the unsaturated polyester contains a polybasic acid having an ethylenically unsaturated double bond in a predetermined proportion.

In the unsaturated polyester resin composition of the present invention, polyvinyl acetate as a low shrinkage agent is in a predetermined ratio with respect to the resin component.

Therefore, a molded article obtained using the unsaturated polyester resin composition is excellent in low shrinkage and flame retardancy.

The unsaturated polyester resin composition of the present invention contains aluminum hydroxide and a flame retardant, and the aluminum hydroxide is in a predetermined ratio with respect to the resin component.

When the compounding ratio of aluminum hydroxide is increased, the linear expansion coefficient of a molded article obtained by using the unsaturated polyester resin composition is decreased, while the flame retardancy is improved, and when the compounding ratio of aluminum hydroxide is decreased, the linear expansion coefficient of the molded article is increased, while the flame retardancy is decreased.

In addition, when the molded article is combined with a light metal, from the viewpoint of improving dimensional stability, if the blending ratio of aluminum hydroxide is adjusted so as to reduce the difference in linear expansion coefficient between the molded article and the light metal, it is not sufficient to ensure flame retardancy.

Therefore, the unsaturated polyester resin composition contains a flame retardant.

As a result, the molded article obtained using the unsaturated polyester resin composition of the present invention is excellent in dimensional stability and flame retardancy.

The molding material of the present invention contains the unsaturated polyester resin composition of the present invention, and therefore, a molded article obtained using the molding material is excellent in low shrinkage, excellent in flame retardancy, and excellent in dimensional stability even when combined with a light metal.

The molded article of the present invention is excellent in low shrinkage and flame retardancy because it contains a cured product of the molding material of the present invention, and is excellent in dimensional stability even when combined with a light metal.

The battery pack case for an electric vehicle according to the present invention is excellent in low shrinkage, excellent in flame retardancy, and excellent in dimensional stability, because it includes the molded article according to the present invention.

Drawings

Fig. 1 is a sectional view showing an embodiment of a battery pack case of an electric vehicle according to the present invention.

Fig. 2 is a sectional view of the battery pack case of the electric vehicle of fig. 1 in which a tray member and a lid member are combined.

Detailed Description

The unsaturated polyester resin composition of the present invention comprises a resin component, aluminum hydroxide and a flame retardant.

The resin component contains an unsaturated polyester, a polymerizable monomer, and a low shrinkage agent.

The unsaturated polyester is a polymerization product of a polybasic acid and a polyhydric alcohol.

The polybasic acid comprises: a polybasic acid having an ethylenically unsaturated double bond (hereinafter referred to as an ethylenically unsaturated bond-containing polybasic acid) as an essential component, and a polybasic acid having no ethylenically unsaturated double bond (hereinafter referred to as an ethylenically unsaturated bond-free polybasic acid) as an optional component.

Examples of the polyvalent acid having an ethylenically unsaturated bond include ethylenically unsaturated aliphatic dibasic acids such as maleic acid, fumaric acid, itaconic acid, and dihydromuconic acid, halides of these acids, and alkyl esters of these acids.

Further, the ethylenically unsaturated bond-containing polybasic acid includes acid anhydrides derived from the above ethylenically unsaturated aliphatic dibasic acid, such as maleic anhydride and the like.

Preferable examples of the ethylenically unsaturated bond-containing polybasic acid include maleic anhydride and fumaric acid.

Examples of the polybasic acid having no ethylenically unsaturated bond include saturated aliphatic polybasic acids, saturated alicyclic polybasic acids, aromatic polybasic acids, halides of these acids, and alkyl esters of these acids.

Examples of the saturated aliphatic polybasic acid include saturated aliphatic dibasic acids such as oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2-dimethylglutaric acid, 3-dimethylsuccinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.

The saturated aliphatic polybasic acid includes acid anhydrides derived from the above saturated aliphatic dibasic acids, for example, oxalic anhydride and succinic anhydride.

Examples of the saturated alicyclic polybasic acid include saturated alicyclic dibasic acids such as a chlorendic acid, 1, 2-hexahydrophthalic acid, 1-cyclobutanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid (cis-or trans-1, 4-cyclohexanedicarboxylic acid or a mixture thereof), and dimer acid.

Examples of the aromatic polybasic acid include aromatic dibasic acids such as phthalic acid (phthalic acid, isophthalic acid, terephthalic acid), trimellitic acid, and pyromellitic acid.

The aromatic polybasic acid includes acid anhydrides derived from the above aromatic dibasic acids, such as phthalic anhydride.

The polybasic acid having no ethylenically unsaturated bond preferably includes an aromatic polybasic acid, more preferably an aromatic dibasic acid, still more preferably phthalic acid, and particularly preferably isophthalic acid.

The polybasic acids may be used alone or in combination of 2 or more.

In the unsaturated polyester, the polybasic acid contains an ethylenically unsaturated bond-containing polybasic acid in a predetermined proportion.

Specifically, when the polybasic acid having an ethylenically unsaturated bond and the polybasic acid having no ethylenically unsaturated bond are used in combination, the blending ratio of the polybasic acid having an ethylenically unsaturated bond to the polybasic acid is 80 mol% or more, and for example, 99 mol% or less.

In addition, when the ethylenically unsaturated bond-containing polybasic acid is used alone, the blending ratio of the ethylenically unsaturated bond-containing polybasic acid to the polybasic acid is 100 mol% (that is, 80 mol% or more).

The ethylenically unsaturated bond-containing polybasic acid is preferably used alone.

In the unsaturated polyester, the polybasic acid contains the ethylenically unsaturated bond-containing polybasic acid in the above range, and therefore such unsaturated polyester has high reactivity.

Examples of the polyhydric alcohol include alkanediols such as ethylene glycol, propylene glycol (1, 2-or 1, 3-propanediol or a mixture thereof), butanediol (1, 2-or 1, 3-or 1, 4-butanediol or a mixture thereof), 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2,2, 2-trimethylpentanediol, 3-dimethylolheptane and the like, aliphatic diols such as ether diols such as diethylene glycol, triethylene glycol, dipropylene glycol and the like, cyclohexanediol (1, 2-or 1, 3-or 1, 4-cyclohexanediol or a mixture thereof), cyclohexanedimethanol (1, 2-or 1, 3-or 1, 4-cyclohexanedimethanol or a mixture thereof), cyclohexanediol (1, 2-or 1, 3-or 1, 4-cyclohexanediol or a mixture thereof), alicyclic diols such as hydrogenated bisphenol A, 2-membered alcohols such as aromatic diols such as bisphenol A, ethylene oxide adducts of bisphenol A, and propylene oxide adducts of bisphenol A, 3-membered alcohols such as glycerol, trimethylolpropane, and triisopropanolamine, 4-membered alcohols such as tetramethylolmethane (pentaerythritol), diethylene glycol, 5-membered alcohols such as xylitol, 6-membered alcohols such as sorbitol, mannitol, allitol, iditol, galactitol, altritol, inositol, and dipentaerythritol, etc., preferably 2-membered alcohols, more preferably, an aliphatic diol, still more preferably an alkanediol, and particularly preferably propylene glycol or neopentyl glycol.

The polyhydric alcohol may be used singly or in combination of 2 or more, and propylene glycol and neopentyl glycol are preferably used in combination.

The unsaturated polyester is obtained by polycondensation (condensation polymerization) of a polybasic acid with a polyhydric alcohol.

When the polybasic acid and the polyhydric alcohol are polycondensed (condensation polymerization), the polyhydric alcohol is blended so that the equivalent ratio of the polyhydric alcohol to the polybasic acid (hydroxyl group of the polyhydric alcohol/carboxyl group of the polybasic acid) is, for example, 0.9 or more, preferably 0.95 or more, and further, for example, 1.2 or less, preferably 1.1 or less, and stirring is performed under normal pressure or a nitrogen atmosphere.

The reaction temperature is, for example, 150 ℃ or higher, preferably 190 ℃ or higher, and is, for example, 250 ℃ or lower, preferably 230 ℃ or lower.

The reaction time is, for example, 8 hours or more, and 30 hours or less.

In the above reaction, a known solvent and a known catalyst may be mixed as necessary.

Thus, an unsaturated polyester was obtained.

The acid value of the unsaturated polyester (measurement method: according to JIS K6901 (2008)), for example, is not less than 20mgKOH/g and less than 40 mgKOH/g.

The unsaturated polyester has a weight average molecular weight of, for example, 6000 or more, preferably 8000 or more, and further, 25000 or less, preferably 20000 or less.

The weight average molecular weight can be determined by GPC (gel permeation chromatography) measurement of the unsaturated polyester, based on the weight average molecular weight in terms of polystyrene of GPC.

The blending ratio of the unsaturated polyester is, for example, 20% by mass or more and, for example, 60% by mass or less with respect to the resin component.

The polymerizable monomer is a solvent for dissolving the unsaturated polyester and is a crosslinkable monomer (reactive diluent) capable of crosslinking with the unsaturated polyester upon curing of an unsaturated polyester resin (described later), and examples thereof include styrene-based monomers such as styrene, α -methylstyrene, α -ethylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate and stearyl (meth) acrylate, allyl (meth) acrylate such as allyl (meth) acrylate, and the like, Examples of the (meth) acrylic acid ester include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and other cyclic structure-containing (meth) acrylic acid esters, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate, aminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, and chloride salts thereof, Examples of the (meth) acrylate monomer include (meth) acrylate monomers such as trifluoroethyl (meth) acrylate and fluoroalkyl (meth) acrylates such as heptadecafluorodecyl (meth) acrylate, polyfunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and allyl monomers such as glycerol monoallyl ether, pentaerythritol diallyl ether, pentaerythritol monoallyl ether and trimethylolpropane monoallyl ether. The (meth) acrylic group is synonymous with a methacrylic group and/or an acrylic group.

The polymerizable monomers may be used singly or in combination of 2 or more.

The blending ratio of the polymerizable monomer is, for example, 20% by mass or more, for example, 60% by mass or less, and preferably 50% by mass or less, relative to the resin component.

The blending ratio of the polymerizable monomer is, for example, 50 parts by mass or more, for example, 200 parts by mass or less, and preferably 100 parts by mass or less, based on 100 parts by mass of the unsaturated polyester.

The low shrinkage agent is compounded for suppressing the curing shrinkage and thermal shrinkage of a molded article (described later) obtained by using the unsaturated polyester resin composition.

The low profile agent comprises polyvinyl acetate as an essential ingredient.

Polyvinyl acetate can suppress curing shrinkage and heat shrinkage of a molded article (described later).

Therefore, when the low shrinkage agent contains polyvinyl acetate, a molded article (described later) obtained using the unsaturated polyester resin composition has excellent low shrinkage properties.

The blending ratio of the polyvinyl acetate is 3 parts by mass or more, preferably 5 parts by mass or more, and 10 parts by mass or less with respect to 100 parts by mass of the resin component.

When the blending ratio of the polyvinyl acetate is not less than the lower limit, a molded article (described later) obtained by using the unsaturated polyester resin composition is excellent in low shrinkage.

On the other hand, when the blending ratio of polyvinyl acetate is less than the lower limit, the low shrinkage property of a molded article (described later) obtained by using the unsaturated polyester resin composition is lowered.

When the blending ratio of the polyvinyl acetate is not more than the upper limit, a molded article (described later) obtained by using the unsaturated polyester resin composition is excellent in low shrinkage.

On the other hand, when the blending ratio of polyvinyl acetate exceeds the upper limit, the film releasability at the time of producing the molding material is lowered, and the production stability is lowered.

The low shrinkage agent contains, as an optional component, other low shrinkage agents such as polystyrene, polyethylene, crosslinked polystyrene, polyvinyl acetate-polystyrene block copolymer, SBS (rubber), and saturated polyester resin.

The saturated polyester resin is obtained by dissolving a saturated polyester in the polymerizable monomer.

The saturated polyester is a polymerization product of the above-mentioned polybasic acid having no ethylenically unsaturated bond and the above-mentioned polyhydric alcohol.

The polybasic acid having no ethylenically unsaturated bond preferably includes a saturated aliphatic polybasic acid and an aromatic polybasic acid, more preferably includes a saturated aliphatic dibasic acid and an aromatic dibasic acid, and still more preferably includes adipic acid and isophthalic acid.

The polybasic acids having no ethylenically unsaturated bond may be used alone or in combination of 2 or more.

The polyol is preferably a 2-membered alcohol, and more preferably neopentyl glycol.

The polyhydric alcohols may be used singly or in combination of 2 or more.

The saturated polyester is obtained by polycondensation (condensation polymerization) of a polybasic acid having no ethylenically unsaturated bond with a polyhydric alcohol.

When the polybasic acid containing no ethylenically unsaturated bond is polycondensed (condensation polymerization) with the polyhydric alcohol, the polyhydric alcohol is blended so that the equivalent ratio of the polyhydric alcohol to the polybasic acid (hydroxyl group of the polyhydric alcohol/carboxyl group of the polybasic acid) becomes, for example, 0.9 or more, preferably 0.95 or more, and further becomes, for example, 1.2 or less, preferably 1.1 or less, and stirring is performed under normal pressure and a nitrogen atmosphere.

The reaction temperature is, for example, 150 ℃ or higher, preferably 190 ℃ or higher, and is, for example, 250 ℃ or lower, preferably 230 ℃ or lower.

The reaction time is, for example, 8 hours or more, and 30 hours or less.

In the above reaction, a known solvent and a known catalyst may be mixed as necessary.

Thus, a saturated polyester was obtained.

The acid value of the saturated polyester (measurement method: according to JIS K6901 (2008)) is, for example, 5mgKOH/g or more and less than 40 mgKOH/g.

Then, the saturated polyester is dissolved in the polymerizable monomer (preferably styrene), and an additive (a polymerization inhibitor (described later) (preferably hydroquinone)) is added as necessary, thereby producing a saturated polyester resin.

In the production of the saturated polyester resin, the blending ratio of the polymerizable monomer is, for example, 35 parts by mass or more and, for example, 150 parts by mass or less with respect to 100 parts by mass of the saturated polyester, and the blending ratio of the polymerization inhibitor is, for example, 0.001 parts by mass or more and, preferably, 0.005 parts by mass or more and, for example, 0.1 parts by mass or less and, preferably, 0.05 parts by mass or less with respect to 100 parts by mass of the saturated polyester.

The low shrinkage agent may be used singly or in combination of 2 or more, and it is preferable to use polyvinyl acetate and a saturated polyester resin in combination.

That is, the low shrinkage agent preferably contains a saturated polyester resin.

The blending ratio of the saturated polyester is, for example, 8 parts by mass or more, preferably 10 parts by mass or more, and, for example, 15 parts by mass or less with respect to 100 parts by mass of the resin component.

The blending ratio of the low shrinkage agent is, for example, 10 mass% or more, preferably 20 mass% or more, and for example, 50 mass% or less with respect to the resin component.

The blending ratio of the low shrinkage agent is, for example, 20 parts by mass or more, preferably 30 parts by mass or more, and for example, 70 parts by mass or less, based on 100 parts by mass of the unsaturated polyester.

The resin component contains other thermosetting resins (excluding unsaturated polyester resins) as required.

Examples of the other thermosetting resin include a vinyl ester resin, a brominated vinyl ester resin, and an acryl resin solution (acrysiriup).

The vinyl ester resin is obtained by dissolving vinyl ester in the polymerizable monomer.

The vinyl ester is the reaction product of a non-brominated epoxy resin and an unsaturated monobasic acid.

The non-brominated epoxy resin is a reaction product of the 1 st phenol component and the 1 st epoxy component.

The 1 st phenol component comprises a non-brominated bisphenol compound.

The non-brominated bisphenol compound is represented by the following general formula (1).

[ chemical formula 1]

(in the formula, Y¹represents-C (CH)₃)₂-、-CH₂-, -O-, -S-, - (O ═ S ═ O) -, and a pharmaceutically acceptable salt thereof. )

Examples of the non-brominated bisphenol compound include bisphenol a, bisphenol F, bisphenol S, and the like, and bisphenol a is preferable.

These non-brominated bisphenol compounds may be used alone or in combination of 2 or more.

The 1 st epoxy component comprises a non-brominated epoxy compound.

The non-brominated epoxy compound is represented by the following general formula (2).

[ chemical formula 2]

(in the formula, Y¹Y is represented by the formula (1)¹The same meaning, n represents an integer of 0 to 5. )

Examples of such a non-brominated epoxy compound include a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type epoxy resin.

The epoxy equivalent of the non-brominated epoxy compound is, for example, 100g/eq or more, preferably 150g/eq or more, and, for example, 800g/eq or less, preferably 400g/eq or less, more preferably less than 300g/eq, and still more preferably 250g/eq or less.

These non-brominated epoxy compounds may be used alone or in combination of 2 or more.

Then, in order to obtain a non-brominated epoxy resin, the 1 st phenol component is reacted with the 1 st epoxy component. Specifically, a non-brominated bisphenol compound and a non-brominated epoxy compound are complexed and reacted.

In the above reaction, a chain extension reaction of a non-brominated bisphenol compound with a non-brominated epoxy compound is carried out.

In the above reaction, the 1 st epoxy component is 0.5 equivalents or more, preferably 1.0 equivalents or more, preferably 2.0 equivalents or more, and for example, 4.0 equivalents or less to 1 equivalent of the 1 st phenol component.

In the above reaction, a catalyst may be added as necessary.

Examples of the catalyst include amines such as triethylamine and benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride and triethylbenzylammonium chloride, imidazoles such as 2-ethyl-4-imidazole, amides such as pyridines, phosphines such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide and ethyltriphenylphosphonium bromide, sulfonium salts such as sulfonic acids, organic metal salts such as zinc octylate, quaternary ammonium salts are preferred, and triethylbenzylammonium chloride is more preferred.

These catalysts may be used alone or in combination of 2 or more.

The mixing ratio of the catalyst is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and is, for example, 3.0 parts by mass or less, preferably 1.0 part by mass or less, relative to 100 parts by mass of the total amount of the 1 st phenol component and the 1 st epoxy component.

In the above reaction, a polymerization inhibitor (described later) (preferably hydroquinone) may be added as necessary.

The mixing ratio of the polymerization inhibitor is, for example, 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and, for example, 0.5 parts by mass or less, preferably 0.1 parts by mass or less, relative to 100 parts by mass of the total amount of the 1 st phenol component and the 1 st epoxy component.

The reaction temperature is, for example, 80 ℃ or higher, preferably 100 ℃ or higher, and 170 ℃ or lower, and the reaction time is, for example, 1 hour or higher, preferably 3 hours or higher, and 12 hours or lower, preferably 10 hours or lower.

Thus, a non-brominated epoxy resin was obtained.

The epoxy equivalent of the non-brominated epoxy resin is, for example, 200g/eq or more, preferably 300g/eq or more, and, for example, 800g/eq or less, preferably 400g/eq or less.

Examples of the unsaturated monobasic acid include monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and sorbic acid, and reaction products of dibasic acid anhydrides and alcohols having at least one unsaturated group in the molecule. Examples of the dibasic acid anhydride include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Examples of the alcohol having an unsaturated group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and glycerol di (meth) acrylate.

The unsaturated monobasic acid may be used alone or in combination of 2 or more.

The unsaturated monobasic acid is preferably a monocarboxylic acid, more preferably (meth) acrylic acid, and still more preferably methacrylic acid.

Then, to obtain the vinyl ester, the non-brominated epoxy resin is reacted with an unsaturated monobasic acid.

In the above reaction, the epoxy group of the non-brominated epoxy resin undergoes an addition reaction with an unsaturated monobasic acid.

In the above reaction, the equivalent of the carboxyl group of the unsaturated monobasic acid to the epoxy group of the non-brominated epoxy resin is, for example, 1 or more, preferably 1.5 or more, and, for example, 2.5 or less.

The reaction temperature is, for example, 80 ℃ or higher, preferably 100 ℃ or higher, and is, for example, 150 ℃ or lower, preferably 130 ℃ or lower, as the reaction conditions, and the reaction time is, for example, 1 hour or longer, preferably 2 hours or longer, and is, for example, 10 hours or shorter.

The above reaction may be carried out following the reaction of the 1 st phenol component and the 1 st epoxy component.

Thus, a vinyl ester was obtained.

The acid value of the vinyl ester (measurement method: according to JIS K6901 (2008)), for example, is 5mgKOH/g to 20 mgKOH/g.

Then, a vinyl ester resin is prepared by dissolving a vinyl ester in the polymerizable monomer (preferably styrene).

The brominated vinyl ester resin is obtained by dissolving a brominated vinyl ester in the above polymerizable monomer.

Brominated vinyl ester resins are the reaction products of brominated epoxy resins with the unsaturated monoacids described above.

The brominated epoxy resin is the reaction product of the 2 nd phenolic component and the 2 nd epoxy component.

The 2 nd phenol component comprises a brominated bisphenol compound.

The brominated bisphenol compound is represented by the following general formula (3).

[ chemical formula 3]

(in the formula, Y¹Y is represented by the formula (1)¹The same meaning, a and b independently represent an integer of 1 to 4)

Examples of such a brominated bisphenol compound include tetrabromobisphenol a ([2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane), dibromobisphenol a, tetrabromobisphenol F, tetrabromobisphenol S, and the like.

These brominated bisphenol compounds may be used alone or in combination of 2 or more.

The 2 nd phenol component contains the above-mentioned non-brominated bisphenol compound as required.

The 2 nd epoxy component comprises a brominated epoxy compound.

The brominated epoxy compound is represented by the following general formula (4).

[ chemical formula 4]

(in the formula, Y¹Y is represented by the formula (1)¹The same meaning, c to f independently represent an integer of 1 to 4, and n represents an integer of 0 to 5. )

Examples of such a brominated epoxy compound include a tetrabromobisphenol a type epoxy resin, a dibromobisphenol a type epoxy resin, a tetrabromobisphenol F type epoxy resin, and a tetrabromobisphenol S type epoxy resin.

The epoxy equivalent of the brominated epoxy compound is, for example, 100g/eq or more, preferably 200g/eq or more, more preferably 300g/eq or more, and, for example, 1000g/eq or less, preferably 600g/eq or less.

These brominated epoxy compounds may be used alone or in combination of 2 or more.

The 2 nd epoxy component contains the above-mentioned non-brominated epoxy compound as required.

Then, in order to obtain a brominated epoxy resin, the 2 nd phenol component is reacted with the 2 nd epoxy component. Specifically, a brominated bisphenol compound, a brominated epoxy compound, a non-brominated bisphenol compound if necessary, and a non-brominated epoxy compound if necessary are combined and reacted.

In the above reaction, a chain extension reaction is carried out between a brominated bisphenol compound, a brominated epoxy compound, a non-brominated bisphenol compound compounded as required, and a non-brominated epoxy compound compounded as required.

In the above reaction, the 2 nd epoxy component is 0.5 equivalent or more, preferably 1.0 equivalent or more, preferably 2.0 equivalents or more, and for example, 4.0 equivalents or less to 1 equivalent of the 2 nd phenol component.

In the above reaction, the above catalyst may be added as necessary.

The catalyst is preferably a quaternary ammonium salt, and more preferably triethylbenzylammonium chloride.

The mixing ratio of the catalyst is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and is, for example, 3.0 parts by mass or less, preferably 1.0 part by mass or less, relative to 100 parts by mass of the total amount of the 2 nd phenol component and the 2 nd epoxy component.

In the above reaction, a polymerization inhibitor (described later) (preferably hydroquinone) may be added as necessary.

The mixing ratio of the polymerization inhibitor is, for example, 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and, for example, 0.5 parts by mass or less, preferably 0.1 parts by mass or less, relative to 100 parts by mass of the total amount of the 2 nd phenol component and the 2 nd epoxy component.

The reaction temperature is, for example, 80 ℃ or higher, preferably 100 ℃ or higher, and 150 ℃ or lower, preferably 130 ℃ or lower, as the reaction conditions, and the reaction time is, for example, 1 hour or higher, preferably 3 hours or higher, and 12 hours or lower, preferably 10 hours or lower.

Thus, a brominated epoxy resin was obtained.

The epoxy equivalent of the brominated epoxy resin is, for example, 200g/eq or more, preferably 300g/eq or more, and, for example, 800g/eq or less, preferably 500g/eq or less.

The bromine content of the brominated epoxy resin is, for example, 20 mass% or more, preferably 30 mass% or more, and, for example, 60 mass% or less.

The bromine content of the brominated epoxy resin can be determined by ion chromatography.

Then, to obtain the brominated vinyl ester, the brominated epoxy resin is reacted with the above-mentioned unsaturated monobasic acid (preferably methacrylic acid).

In the above reaction, the epoxy group of the brominated epoxy resin undergoes an addition reaction with an unsaturated monobasic acid.

In the above reaction, the equivalent of the carboxyl group of the unsaturated monobasic acid to the epoxy group of the brominated epoxy resin is, for example, 0.5 or more, preferably 1.0 or more, and, for example, 2.5 or less.

The reaction temperature is, for example, 80 ℃ or higher, preferably 100 ℃ or higher, and 150 ℃ or lower, preferably 130 ℃ or lower, as the reaction conditions, and the reaction time is, for example, 1 hour or higher, preferably 2 hours or higher, and 10 hours or lower, preferably 6 hours or lower.

The above reaction may be carried out following the reaction of the above-mentioned 2 nd phenol component and 2 nd epoxy component.

Thus, a brominated vinyl ester was obtained.

The acid value of the brominated vinyl ester (measurement method: in accordance with JIS K6901 (2008)) is, for example, 5mgKOH/g to 20 mgKOH/g.

Then, a brominated vinyl ester resin is prepared by dissolving a brominated vinyl ester in the above polymerizable monomer (preferably styrene).

The bromine content of the brominated vinyl ester resin is, for example, 10 mass% or more, preferably 20 mass% or more, and, for example, 40 mass% or less.

The bromine content of the brominated vinyl ester resin can be determined by ion chromatography.

The blending ratio of the other thermosetting resin is, for example, 15 mass% or more and, for example, 40 mass% or less with respect to the resin component.

The aluminum hydroxide is added to a molded article (described later) obtained using the unsaturated polyester resin composition in order to impart flame retardancy, transparency, and color scales to the molded article (described later) and to adjust the linear expansion coefficient of the molded article (described later).

The average particle diameter of the aluminum hydroxide is, for example, 1 μm or more, and is, for example, 50 μm or less, preferably 25 μm or less.

The average particle size of the aluminum hydroxide can be determined as follows: a particle size distribution curve was prepared by a laser diffraction/scattering particle size distribution measuring apparatus, and the particle size corresponding to 50 mass% was calculated and determined.

The aluminum hydroxide may be used alone, or 2 or more types of aluminum hydroxide having different average particle diameters and different sodium oxide contents may be used in combination.

The blending ratio of the aluminum hydroxide is 50 parts by mass or more, preferably 60 parts by mass or more, and less than 150 parts by mass, more preferably 125 parts by mass or less, and further preferably 115 parts by mass or less with respect to 100 parts by mass of the resin component.

When the compounding ratio of aluminum hydroxide is increased, the linear expansion coefficient of a molded article (described later) obtained by using the unsaturated polyester resin composition is decreased, while the flame retardancy is improved, and when the compounding ratio of aluminum hydroxide is decreased, the linear expansion coefficient of a molded article (described later) obtained by using the unsaturated polyester resin composition is increased, while the flame retardancy is decreased.

In the case where a molded article (described later) obtained by using the unsaturated polyester resin composition is combined with a light metal, the blending ratio of aluminum hydroxide is adjusted to the above range in order to reduce the difference in linear expansion coefficient with the light metal from the viewpoint of improving dimensional stability. Therefore, when the blending ratio of aluminum hydroxide is within the above range, a molded article (described later) obtained using the unsaturated polyester resin composition has excellent dimensional stability even when combined with a light metal (described later).

On the other hand, when the blending ratio of aluminum hydroxide is less than the lower limit, dimensional stability of a molded article (described later) obtained using the unsaturated polyester resin composition is lowered and flame retardancy is excessively lowered when the molded article is combined with a light metal (described later).

When the blending ratio of aluminum hydroxide exceeds the upper limit, dimensional stability of a molded article (described later) obtained using the unsaturated polyester resin composition is lowered when the molded article is combined with a light metal (described later).

Further, dimensional stability can be improved only by adjusting the compounding ratio of aluminum hydroxide within the above range, but the securing of flame retardancy is insufficient (specifically, in the UL94 flame retardancy test (thickness 3mm), V-0 standard cannot be satisfied). Therefore, the unsaturated polyester resin composition contains a flame retardant (described later).

The molded article (described later) obtained using the unsaturated polyester resin composition does not necessarily satisfy the 5VA standard which is a flame retardant standard higher than the V-0 standard, depending on the purpose and use.

The flame retardant is blended for imparting flame retardancy to a molded article (described later) obtained by using the unsaturated polyester resin composition, and more specifically, it is blended for satisfying the above-mentioned V-0 standard because it is not satisfied in the UL94 flame retardancy test (thickness 3mm) only by blending aluminum hydroxide in the above-mentioned blending ratio as described above.

Examples of the flame retardant include halogen flame retardants such as bromine flame retardants, non-halogen flame retardants such as phosphorus flame retardants, inorganic flame retardants, and nitrogen compound flame retardants.

Examples of the bromine-based flame retardant include hexabromobenzene, tetrabromobisphenol, bromobiphenyl such as tetrabromobiphenyl, hexabromobiphenyl, decabromobiphenyl and decabromodiphenylethane (bispentabromophenylethane), and bromodiphenylether such as tetrabromodiphenyl ether, hexabromodiphenyl ether and decabromodiphenyl ether.

Examples of the phosphorus-based flame retardant include red phosphorus, phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tricresyl phosphate, polyphosphate salts such as ammonium polyphosphate, ifr (intumescent) type flame retardants obtained by blending an auxiliary agent such as ammonium polyphosphate and pentaerythritol, and a carbon supplying agent such as melamine, and metal phosphonate salts.

Further, commercially available phosphorus-based flame retardants can be used, and specific examples thereof include the Exolit AP series (specifically, Exolit AP422 (ammonium polyphosphate)), the OP series (specifically, Exolit OP1230 (metal phosphonate)), and the RP series (Clariant Chemicals).

Examples of the inorganic flame retardant include antimony oxides such as antimony trioxide, zinc stannate, zinc borate, and preparations thereof, and preferably antimony trioxide is used.

Examples of the nitrogen compound-based flame retardant include azoalkane compounds, hindered amine compounds, and melamine compounds.

The flame retardant is preferably a non-halogen flame retardant.

That is, the unsaturated polyester resin composition preferably contains substantially no halogen-based flame retardant.

The substantially halogen-free flame retardant means that the halogen-containing flame retardant is, for example, 1.0 mass% or less, preferably 0.1 mass% or less, relative to the unsaturated polyester resin composition.

When the unsaturated polyester resin composition does not substantially contain a halogen-based flame retardant, generation of a gas derived from halogen during combustion can be suppressed, and environmental pollution can be suppressed.

Further, as the flame retardant, a phosphorus-based flame retardant is more preferable, a phosphoric ester is further preferable, and ammonium polyphosphate and a metal phosphonate are particularly preferable.

That is, it is more preferable that the unsaturated polyester resin composition contains a phosphorus-based flame retardant.

When the unsaturated polyester resin composition contains a phosphorus flame retardant, the flame retardancy can be improved.

The blending ratio of the flame retardant is, for example, 5 parts by mass or more, preferably 15 parts by mass or more, preferably 25 parts by mass or more, and is, for example, 100 parts by mass or less, preferably 50 parts by mass or less, with respect to 100 parts by mass of the resin component.

The blending ratio of the flame retardant is, for example, 3 parts by mass or more, preferably 5 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more, and is, for example, 80 parts by mass or less, preferably 70 parts by mass or less, and more preferably 50 parts by mass or less, with respect to 100 parts by mass of aluminum hydroxide.

When the blending ratio of the flame retardant is not less than the lower limit, the flame retardancy is excellent.

When the blending ratio of the flame retardant is not more than the upper limit, the flame retardancy is excellent, and the reinforcing fiber can be sufficiently impregnated in the unsaturated polyester resin composition, so that the production stability is excellent.

The flame retardants may be used singly or in combination of 2 or more.

Then, the unsaturated polyester resin composition can be obtained by blending the resin component, aluminum hydroxide and flame retardant in the blending ratio described above. Specifically, the unsaturated polyester, the polymerizable monomer, the low shrinkage agent, another thermosetting resin if necessary, aluminum hydroxide, and the flame retardant are blended in the above blending ratio.

Thus, an unsaturated polyester resin composition was obtained.

In such an unsaturated polyester resin composition, the blending ratio of the resin component is, for example, 30% by mass or more, preferably 40% by mass or more, and, for example, 60 parts by mass or less with respect to the unsaturated polyester resin composition. The blending ratio of the aluminum hydroxide is 20 mass% or more, for example, 60 parts by mass or less and 40 mass% or less with respect to the unsaturated polyester resin composition. The blending ratio of the flame retardant is, for example, 1 mass% or more, preferably 5 mass% or more, and is, for example, 20 mass% or less. The total amount of the resin component, aluminum hydroxide and the flame retardant is, for example, 95 mass% or more and, for example, 100 mass% or less with respect to the unsaturated polyester resin composition.

Further, additives such as a polymerization inhibitor, a curing agent, a release agent, a colorant, a filler, and a thickener may be added to the unsaturated polyester resin composition as needed. These additives may be used singly or in combination of 2 or more.

The polymerization inhibitor is added for adjusting the pot life and the curing reaction, and examples thereof include hydroquinone compounds such as hydroquinone, methylhydroquinone and tert-butylhydroquinone, quinone compounds such as p-benzoquinone and methyl-p-benzoquinone, catechol compounds such as tert-butylcatechol, phenol compounds such as 2, 6-di-tert-butyl-4-methylphenol and 4-methoxyphenol, 1-oxyl-2,2,6, 6-tetramethylpiperidine (1-oxyl-2,2,6, 6-tetramethylpiperidine), 1-oxyl-2,2,6, 6-tetramethylpiperidin-4-ol, 4-hydroxy-2, 2,6, 6-tetrapiperidin-1-oxyl and 4-methoxy-2, 2,6, 6-tetramethylpiperidin-1-yloxy radical, 1-oxy radical-2, 2,6, 6-tetramethylpiperidin-4-yl-acetate, 1-oxy radical-2, 2,6, 6-tetramethylpiperidin-4-yl-2-ethylhexanoate, 1-oxy radical-2, 2,6, 6-tetramethylpiperidin-4-yl-stearate, 1-oxy radical-2, 2,6, 6-tetramethylpiperidin-4-yl-4-tert-butylbenzoate, bis (1-oxy radical-2, 2,6, 6-tetramethylpiperidin-4-yl) succinate, bis (1-oxy radical-2, 2,6, 6-tetramethylpiperidin-4-yl) adipate, bis (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) sebacate, bis (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) n-butylmalonate, bis (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) phthalate, bis (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) isophthalate, bis (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) terephthalate, bis (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N' -bis (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) adipamide, N-bis (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) caprolactam, N-bis (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) dodecylsuccinimide, 2,4, 6-tris- [ N-butyl-N- (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) ] -s-triazine, 1-oxyl-2, the N-oxyl compound such as 2,6, 6-tetramethylpiperidin-4-one is preferably a benzoquinone compound, more preferably p-benzoquinone.

The mixing ratio of the polymerization inhibitor is, for example, 0.01 parts by mass or more and, for example, 0.1 parts by mass or less with respect to 100 parts by mass of the resin component.

The polymerization inhibitor may be used singly or in combination of 2 or more.

Examples of the curing agent include peroxides such as benzoyl peroxide, t-butylperoxyisopropyl monocarbonate, t-amylperoxyisopropyl monocarbonate, t-hexylperoxyisopropyl monocarbonate, 1-bis (t-butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexanoate, amyl peroxy-2-ethylhexanoate, 2-ethylhexyl peroxy-2-ethylhexanoate, t-butylperoxybenzoate, t-hexylperoxybenzoate, and t-hexylperoxyacetate, and preferably include t-butylperoxyisopropyl monocarbonate, t-amylperoxyisopropyl monocarbonate, t-hexylperoxyisopropyl monocarbonate, and t-butylperoxybenzoate as the peroxyisopropyl monocarbonate.

The mixing ratio of the curing agent is, for example, 0.5 parts by mass or more, preferably 0.8 parts by mass or more, and is, for example, 10 parts by mass or less, preferably 3 parts by mass or less, with respect to 100 parts by mass of the resin component.

The curing agent may be used singly or in combination of 2 or more.

Examples of the release agent include fatty acids such as stearic acid and lauric acid, fatty acid metal salts such as zinc stearate and calcium stearate, paraffin wax, liquid wax, fluoropolymers, and silicone polymers, and preferably include fatty acid metal salts, and more preferably include zinc stearate.

The compounding ratio of the release agent is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and, for example, 10 parts by mass or less, with respect to 100 parts by mass of the resin component.

The release agent may be used singly or in combination of 2 or more.

The colorant is not particularly limited, and examples thereof include titanium oxide, a polyester toner (toner) (a polyester colorant containing titanium oxide and/or carbon black), and the like, and preferably include a polyester toner.

The blending ratio of the colorant is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and, for example, 20 parts by mass or less, with respect to 100 parts by mass of the resin component.

The coloring agent may be used singly or in combination of 2 or more.

Examples of the filler include oxides such as alumina and titanium dioxide, hydroxides such as magnesium hydroxide (excluding aluminum hydroxide), carbonates such as calcium carbonate, sulfates such as barium sulfate, hollow fillers such as glass powder, glass spheres, silica spheres, and alumina spheres, silicates such as silica sand, diatomaceous earth, mica, clay, kaolin, and talc, fluorides such as fluorite, phosphates such as calcium phosphate, and inorganic fillers such as clay minerals such as montmorillonite.

The mixing ratio of the filler is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, with respect to 100 parts by mass of the resin component.

The filler may be used singly or in combination of 2 or more.

The wetting dispersant is added to the unsaturated polyester resin composition to reduce the viscosity thereof to a level suitable for compression molding under heating, and examples thereof include known wetting dispersants such as phosphoric acid polyesters. As the wetting dispersant, a commercially available one can be used, and specifically, BYK-W996(BYK corporation) and the like can be used.

The blending ratio of the wetting dispersant is, for example, 0.1 part by mass or more and, for example, 10 parts by mass or less with respect to 100 parts by mass of the resin component.

The wetting dispersant may be used singly or in combination of 2 or more.

The thickener is added to thicken the unsaturated polyester resin composition to a viscosity suitable for compression molding under heating, and is preferably added before (preferably immediately before) impregnation of the reinforcing fiber (described later) with the unsaturated polyester resin composition, and examples thereof include alkaline earth metal oxides such as magnesium oxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, preferably alkaline earth metal oxides, and more preferably magnesium oxide.

The blending ratio of the thickener is, for example, 0.5 parts by mass or more, and is, for example, 10 parts by mass or less, preferably 3 parts by mass or less, with respect to 100 parts by mass of the resin component.

The thickener may be used singly or in combination of 2 or more.

Further, in the unsaturated polyester resin composition, additives such as a pattern material (patterning material), an antibacterial agent, a hydrophilic agent, a photocatalyst, an ultraviolet absorber, an ultraviolet stabilizer, a separation preventing agent, a silane coupling agent, an antistatic agent, a thixotropic stabilizer, and a polymerization accelerator may be blended as necessary within a range not to impair the effects of the present invention. These additives may be used singly or in combination of 2 or more.

In the above description, the unsaturated polyester resin composition is obtained by blending the unsaturated polyester, the polymerizable monomer, the low shrinkage agent, if necessary, another thermosetting resin, aluminum hydroxide, the flame retardant, and if necessary, the additive, but it can also be obtained by: first, an unsaturated polyester resin is prepared by dissolving an unsaturated polyester in a polymerizable monomer, and then the obtained unsaturated polyester resin, the polymerizable monomer, a low shrinkage agent, another thermosetting resin if necessary, aluminum hydroxide, and an additive if necessary are blended.

In the production of the unsaturated polyester resin, the unsaturated polyester and the polymerizable monomer may be blended together with the above-mentioned additive (for example, polymerization inhibitor) as necessary.

In the production of the unsaturated polyester resin, the blending ratio of the polymerizable monomer is, for example, 35 parts by mass or more and, for example, 150 parts by mass or less with respect to 100 parts by mass of the unsaturated polyester, and the blending ratio of the polymerization inhibitor is, for example, 0.001 parts by mass or more and, preferably, 0.005 parts by mass or more and, for example, 0.1 parts by mass or less and, preferably, 0.05 parts by mass or less with respect to 100 parts by mass of the unsaturated polyester.

Then, a molding material can be prepared by adding known reinforcing fibers such as glass fibers to the unsaturated polyester resin composition. Further, a molded article can be obtained from such a molding material by a known method.

Examples of the reinforcing fibers include inorganic fibers such as glass fibers, carbon fibers, metal fibers, and ceramic fibers, organic fibers such as polyvinyl alcohol fibers, polyester fibers, polyamide fibers, fluororesin fibers, and phenol fibers, natural fibers such as hemp and kenaf fibers, and the like.

Examples of the shape of these reinforcing fibers include a cloth shape such as a roving cloth, a chopped strand mat, a pre-form mat (pre-form mat), a continuous strand mat (continuous strand mat), a mat shape such as a surfacing mat, a strand shape, a roving shape, a nonwoven fabric shape, and a paper shape, and preferably a roving shape.

Among these reinforcing fibers, carbon fibers and glass fibers are preferable, glass fibers are more preferable, glass rovings are more preferable, and chopped glass (chopped glass) obtained by cutting glass rovings into pieces having a predetermined length is more preferable.

The length of the reinforcing fiber is not particularly limited, and is, for example, 1.5mm or more, and when a molding material is produced using the unsaturated polyester resin composition, smoothness can be ensured even if the reinforcing fiber is long, and therefore, from the viewpoint of improving strength, the length is preferably 5mm or more, more preferably 15mm or more, and is, for example, 80mm or less, preferably 40mm or less.

Then, the molding material is obtained, for example, in the form of a sheet-like molding material by impregnating the reinforcing fibers with the unsaturated polyester resin composition.

The blending ratio of the reinforcing fibers (for example, when the reinforcing fibers are glass fibers, the content is hereinafter referred to as the glass content ratio) is, for example, 5 mass% or more, preferably 10 mass% or more, and for example, 50 mass% or less, preferably 35 mass% or less, with respect to the total amount of the unsaturated polyester resin composition and the reinforcing fibers.

As a method for producing the molding material, known methods are exemplified, and SMC (sheet molding compound), TMC (thick molding compound), BMC (bulk molding compound) and the like are exemplified, and SMC and TMC suitable for a method for producing a molding material containing long reinforcing fibers (for example, 5mm or more) are preferably exemplified from the viewpoint of improving the strength of a molded product.

Thus, a molding material comprising the unsaturated polyester resin composition and reinforcing fibers was obtained.

In the unsaturated polyester resin composition, the total amount (volume content) of the components other than the filler (specifically, the total amount of the resin component, the flame retardant, and other additives other than the filler, which is blended as necessary) other than the aluminum hydroxide and the filler blended as necessary is, for example, 40 vol% or more, preferably 50 vol% or more, more preferably 55 vol% or more, further preferably 60 vol% or more, and, for example, 70 vol% or less with respect to the molding material.

When the volume content of the filler-excluding component is not less than the lower limit and not more than the upper limit, the unsaturated polyester resin composition can be sufficiently impregnated with the reinforcing fiber, and the production stability is excellent.

The volume content of aluminum hydroxide with respect to the molding material is, for example, 10 vol% or more, and is, for example, 30 vol% or less, preferably 20 vol% or less.

The volume content of the reinforcing fibers in the molding material is, for example, 15 vol% or more, for example, 40 vol% or less, and preferably 30 vol% or less.

Since the molding material contains the unsaturated polyester resin composition, a molded article obtained using the molding material is excellent in low shrinkage, flame retardancy, and dimensional stability even when combined with a light metal.

Next, in order to thicken the molding material so as to enable heating compression molding (described later), it is preferable to perform aging under conditions of, for example, 20 ℃ to 50 ℃ and 8 hours to 120 hours.

Thereby, the molding material is held in a sheet form, for example. That is, the molding material has a sheet-like shape.

Then, the molded article is obtained by subjecting the molding material to heating compression molding by a known method.

The conditions for the heating compression molding are appropriately set according to the purpose and application, and specifically, the molding temperature is, for example, 100 ℃ or higher, and, for example, 200 ℃ or lower, and the molding pressure is, for example, 0.1MPa or higher, preferably 1MPa or higher, more preferably 5MPa or higher, and, for example, 20MPa or lower, preferably 15MPa or lower.

Thereby, the molding material is cured, and the molding material is molded.

Thus, a molded article was obtained.

The molded article contains a cured product of the above molding material, and therefore has excellent low shrinkage and excellent flame retardancy.

In the unsaturated polyester resin composition, the polybasic acid contains an ethylenically unsaturated bond-containing polybasic acid in the above-mentioned predetermined ratio. The unsaturated polyester resin composition contains polyvinyl acetate in the above-mentioned predetermined ratio. Further, by containing aluminum hydroxide at the above-mentioned predetermined ratio, the linear expansion coefficient of the molded article can be approximated to that of a light metal such as aluminum (linear expansion coefficient 23.0 ppm/DEG C) or magnesium (linear expansion coefficient 25.4 ppm/DEG C), and the dimensional stability of the molded article can be improved.

Specifically, the molded article has a linear expansion coefficient of, for example, 20.0 ppm/DEG C or more, preferably 21.5 ppm/DEG C or more, and further, 30.0 ppm/DEG C or less, preferably 28.0 ppm/DEG C or less, preferably 25.0 ppm/DEG C or less.

When the light metal is aluminum, the absolute value of the difference between the linear expansion coefficient of the molded article and the linear expansion coefficient of aluminum (linear expansion coefficient of aluminum-linear expansion coefficient of the molded article) is, for example, 2 or less, preferably 1.3 or less.

In particular, when a molded product is integrally molded with aluminum, as in a lithium battery pack case for an electric vehicle, the influence of the difference tends to become more significant.

However, since the difference between the linear expansion coefficient of the molded article and the linear expansion coefficient of aluminum can be made to be within the above range, the molded article has excellent dimensional stability even when it is integrally molded with aluminum.

On the other hand, molded articles formed from the molding material containing calcium carbonate as disclosed in patent document 1 have a linear expansion coefficient of not less than 0 ppm/DEG C and not more than 16 ppm/DEG C, and have a large difference from light metals (for example, aluminum (linear expansion coefficient of 23.0 ppm/DEG C)). Therefore, when such a molded article is combined with a light metal, there are problems that dimensional stability is poor, such as a change in a gap between members due to a dimensional difference caused by a thermal change, generation of stress in a joint portion, and reduction in sealability at a seal portion.

Examples of the light metal include aluminum and magnesium, and aluminum is preferably used.

The method for measuring the linear expansion coefficient of the molded article is described in detail in examples described later.

Such a molded product is preferably used for a battery pack case of an electric vehicle, and more preferably for a lithium battery pack case of an electric vehicle.

As shown in fig. 1, a battery pack case 1 of an electric vehicle includes a tray member 2 and a lid member 3 combined with the tray member 2.

The tray member 2 is a container for housing a battery (not shown), and includes an inner layer 4, which is an aluminum member, and an outer layer 5, which is the molded article described above, laminated on the inner layer 4.

The inner layer 4 has a box shape with one side open. In addition, the inner layer 4 is formed of aluminum.

The outer layer 5 has a box shape with one side opened similarly to the inner layer 4, and has a size and a shape that can accommodate the inner layer 4 inside (that is, the shape and the size of the inside of the outer layer 5 are the same as the shape and the size of the outside of the inner layer 4). Further, the inner side surfaces (inner circumferential surface and inner bottom surface) of the outer layer 5 are in contact with (closely attached to) the outer side surfaces (outer circumferential surface and outer bottom surface) of the inner layer 4. The outer layer 5 is formed of the molded article described above.

Then, the tray member 2 is obtained by integrally molding the inner layer 4 and the outer layer 5 into the above-described shape.

Specifically, the inner layer 4 is molded into the above-described shape in advance, the above-described molding material is injected around the inner layer 4, and then the molding material is heated and compressed under the above-described conditions, whereby the inner layer 4 and the outer layer 5 are integrated. That is, in the battery pack case 1 of the electric vehicle, the tray member 2 integrally includes the aluminum member and the molded article described above.

Further, as described above, the molded article has excellent dimensional stability because the difference between the linear expansion coefficient of the molded article and the linear expansion coefficient of aluminum is small.

The cover member 3 has a plate shape that closes an opening provided in the tray member 2, and has the same size as the opening. The cover member 3 is formed of the molded article described above.

In the battery pack case 1 of the electric vehicle, as shown in fig. 2, the tray member 2 and the cover member 3 are combined so that the opening provided in the tray member 2 is closed by the cover member 3.

That is, in the battery pack case 1 of the electric vehicle, the molded product is combined with an aluminum member.

Further, as described above, the molded article has excellent dimensional stability because the difference between the linear expansion coefficient of the molded article and the linear expansion coefficient of aluminum is small.

Further, since the battery pack case 1 of the electric vehicle includes the cover member 3 formed of the molded product and the outer layer 5 formed of the molded product, it is excellent in low shrinkage and excellent in flame retardancy.

Examples

Specific numerical values such as the blending ratio (content ratio), the physical property value, and the parameter used in the following description may be replaced with upper limit values (numerical values defined as "lower" and "lower") or lower limit values (numerical values defined as "upper" and "lower") described in association with the above-described blending ratio (content ratio), physical property value, and parameter described in the above-described "embodiment". In the following description, "part" and "%" are based on mass unless otherwise specified.

1. Preparation of unsaturated polyester resins

Synthesis example 1

10.0 mol of maleic anhydride, 6.5 mol of propylene glycol and 4.0 mol of neopentyl glycol were put into a flask equipped with a thermometer, a nitrogen inlet tube, a reflux condenser and a stirrer, and a polycondensation reaction was carried out at 200 to 210 ℃ while stirring in a nitrogen atmosphere, whereby an unsaturated polyester having an acid value of 26.5mgKOH/g was obtained. The method for measuring the acid value was according to JIS K6901 (2008). To 100 parts by mass of the obtained unsaturated polyester, 0.01 part by mass of hydroquinone and 66.7 parts by mass of styrene as polymerization inhibitors were added and uniformly mixed to obtain an unsaturated polyester resin (styrene content: 40%).

Synthesis example 2

3.3 mol of isophthalic acid and 10.5 mol of propylene glycol were put into a flask equipped with a thermometer, a nitrogen inlet, a reflux condenser and a stirrer, and polycondensation reaction was carried out at 200 to 210 ℃ while stirring in a nitrogen atmosphere. Then, when the acid value of the reaction product became 20mgKOH/g, it was cooled to 150 ℃, 6.7 moles of maleic anhydride were added, and the reaction was carried out again at 210 ℃ to 220 ℃ to obtain an unsaturated polyester having an acid value of 27.5 mgKOH/g. To 100 parts by mass of the obtained unsaturated polyester, 0.01 part by mass of hydroquinone and 66.7 parts by mass of styrene as polymerization inhibitors were added and uniformly mixed to obtain an unsaturated polyester resin (styrene content: 40%).

2. Preparation of saturated polyester resin

Synthesis example 3

In a flask equipped with a thermometer, a nitrogen inlet tube, a reflux condenser and a stirrer, 4.0 moles of isophthalic acid and 10.5 moles of neopentyl glycol were charged, and polycondensation reaction was carried out at 200 to 210 ℃ while stirring in a nitrogen atmosphere. Then, when the acid value of the reaction product became 10mgKOH/g, it was cooled to 150 ℃, 6.0 moles of adipic acid were added, and the reaction was carried out again at 210 ℃ to 220 ℃ to obtain a saturated polyester having an acid value of 9.5 mgKOH/g. To 100 parts by mass of the obtained saturated polyester, 0.01 part by mass of hydroquinone and 66.7 parts by mass of styrene as polymerization inhibitors were added and uniformly mixed to obtain a saturated polyester resin (styrene content: 40%).

3. Preparation of vinyl ester resins

Synthesis example 4

Into a flask equipped with a stirrer, a reflux condenser and a gas inlet tube, 114 parts by mass (1.0 equivalent) of bisphenol a, 555 parts by mass (3.0 equivalents) of bisphenol a type epoxy resin (epoxy equivalent 185) and 0.15 parts by mass of triethylbenzylammonium chloride as a catalyst were charged, and a reaction was carried out at 150 ℃ for 5 hours while blowing nitrogen gas, to obtain a non-brominated epoxy resin having an epoxy equivalent of 335. After cooling to 120 ℃ and adding 0.10 part by mass of hydroquinone as a polymerization inhibitor, 1.50 parts by mass of triethylbenzylammonium chloride as a catalyst and 176 parts by mass of methacrylic acid (2.05 equivalents), the reaction was carried out at 110 ℃ for 8 hours while blowing air to obtain a vinyl ester having an acid value of 8.5 mgKOH/g. Subsequently, to the vinyl ester, styrene 563 part by mass was added to obtain a vinyl ester resin containing 40% by mass of styrene.

4. Preparation of brominated vinyl ester resins

Synthesis example 5

In a reaction vessel similar to that of Synthesis example 3, 400 parts by mass (1.0 equivalent) of tetrabromobisphenol A type epoxy resin (epoxy equivalent 400, bromine content 48.0%) as a brominated epoxy resin, 88.2 parts by mass (1.025 equivalent) of methacrylic acid, 0.05 part by mass of hydroquinone as a polymerization inhibitor, and 0.5 part by mass of triethylbenzylammonium chloride as a catalyst were charged, and a reaction was carried out at 110 ℃ for 8 hours while blowing air to obtain a vinyl bromide having an acid value of 9.0 mgKOH/g. Subsequently, 325 parts by mass of styrene was added to the brominated vinyl ester to obtain a brominated vinyl ester resin containing 40% by mass of styrene (bromine content 23.6%).

5. Unsaturated polyester resin composition and production of molding material

Example 1

60 parts by mass (36 parts by mass of an unsaturated polyester, 24 parts by mass of styrene) of the unsaturated polyester resin of Synthesis example 1, 15 parts by mass (6 parts by mass of polyvinyl acetate, 9 parts by mass of styrene) of a polyvinyl acetate solution (40% styrene solution of polyvinyl acetate) as a low shrinkage agent, and 20 parts by mass (12 parts by mass of a saturated polyester, 8 parts by mass of styrene) of the saturated polyester resin of Synthesis example 3,5 parts by mass of styrene as a polymerizable monomer, 10 parts by mass of a metal phosphonate (OP (trade name, Exolit OP1230, phosphorus content 23%) as a flame retardant), 0.05 parts by mass of p-benzoquinone as a polymerization inhibitor, 1.0 part by mass of t-butyl peroxybenzoate as a curing agent, 5 parts by mass of zinc stearate as a mold release agent, 10 parts by mass of a black polyester toner (obtained by dispersing carbon black in a polyester resin) as a coloring agent, and the like were mixed, and the mixture was subjected to the above-described, 130 parts by mass of aluminum hydroxide (average particle diameter: 8 μm) and 1 part by mass of phosphoric polyester as a wetting dispersant were mixed to obtain an unsaturated polyester resin composition.

To the unsaturated polyester resin composition, 0.8 part by mass of magnesium oxide as a thickener was added, and then, as a reinforcing fiber, chopped glass obtained by continuously cutting a glass roving into 25mm pieces was added so that the glass content became 29.5% by mass, and after obtaining a molding material (SMC) by a known SMC dip machine, the molding material was aged at 40 ℃ for 48 hours to thicken the molding material to a state capable of being compression-molded under heating.

Examples 2 to 9 and comparative examples 1 to 7

A molding material was obtained in the same manner as in example 1, except that the formulation was changed as shown in Table 1 and Table 2.

In examples 5 and 9, ammonium polyphosphate (trade name, Exolit AP422, manufactured by Clariant Chemicals, phosphorus content 31%) was used as a flame retardant.

In example 6 and example 8, the vinyl ester resin of synthesis example 4 was used.

In addition, in example 7, the brominated vinyl ester resin of synthesis example 5 was used.

In comparative example 2, a polystyrene solution (a 35% styrene solution of polystyrene having a weight average molecular weight of about 250000) and a polyethylene powder (a polyethylene powder having an average particle size of about 30 μm) were used as the low shrinkage agent.

In comparative example 5, calcium carbonate having an average particle size of about 3 μm was used as a filler.

6. Evaluation of

(Molding shrinkage factor)

The molding material was heated and compression molded using a 300mm × 300mm flat mold to obtain a flat molded article having a thickness of 4 mm.

The molding was carried out under conditions of mold temperature 140 ℃ on the front and back surfaces of the article, molding pressure 10MPa, and mold internal holding time 420 seconds. Then, the molded product was released from the mold and immediately sandwiched between iron plates for cooling. Then, the molded article was left at 25 ℃ for 24 hours, and the dimensions of 4 sides of the molded article at 25 ℃ were measured, and the shrinkage ratio was measured from the ratio to the dimensions of the flat mold. The results are shown in tables 3 and 4.

The degree of shrinkage was evaluated according to the following criteria. The results are shown in tables 3 and 4.

Evaluation criteria:

very good: the shrinkage rate is 0 or less.

O: the shrinkage ratio is 0 or more and less than 0.10.

X: the shrinkage rate is 0.10 or more.

(flame retardancy)

The molding material was molded in the same manner as in the molding shrinkage determination of the flat plate to obtain molded plates having a thickness of 4mm, 3mm and 2.5 mm. Test pieces were cut out from the molded plate, and a burning test was carried out in accordance with UL94 standard (flammability test of plastic material) of UL standard (Underwriters Laboratories Inc.). Each test piece having a thickness of 4mm, a thickness of 3mm and a thickness of 2.5mm was evaluated as to whether it satisfied the V-0 standard. The results are shown in tables 3 and 4.

Further, regarding flame retardancy, the superiority and inferiority were evaluated according to the following criteria. The results are shown in tables 3 and 4.

Evaluation criteria:

very good: meeting the V-0 standard (thickness 2.5 mm).

O: according to the V-0 reference (thickness 3 mm).

X: not conforming to the V-0 reference (thickness 4 mm).

(coefficient of linear expansion)

A test piece (4 mm. times.4 mm. times.5 mm) was cut from a flat plate-shaped molded article (thickness 4mm) used for measurement of the molding shrinkage, and the linear expansion coefficient in the horizontal direction of the molded article was measured using a compression/expansion probe with a thermomechanical analyzer (manufactured by Hitachi High-Tech Science Corporation, EXSTAR TMA SS 7100). The temperature was raised from room temperature to 100 ℃ at a temperature raising rate of 5 ℃/min, and the linear expansion coefficient in the range of 50 ℃ to 80 ℃ was measured. The results are shown in tables 3 and 4.

The obtained linear expansion coefficients and the difference in the linear expansion coefficient of aluminum (23.0 ppm/DEG C) are shown in tables 3 and 4.

The linear expansion coefficient was evaluated for superiority and inferiority according to the following criteria. The results are shown in tables 3 and 4.

Very good: the absolute value of the difference between the linear expansion coefficient of the aluminum and the linear expansion coefficient of the aluminum is more than 0 and less than 1.2

O: the absolute value of the difference between the linear expansion coefficient of the aluminum and the coefficient of linear expansion of the aluminum is more than 1.2 and less than 2

And (delta): the absolute value of the difference between the linear expansion coefficient of the aluminum and the coefficient of linear expansion of the aluminum is more than 2 and less than 4

X: the absolute value of the difference between the linear expansion coefficient of the aluminum and the linear expansion coefficient of the aluminum is more than 4

(fuming property)

In the above flame retardancy test, whether black smoke is generated during combustion was visually observed in a V-0 determination test when a test piece having a thickness of 3mm was used.

The fuming property was evaluated as follows. The results are shown in tables 3 and 4.

O: no black smoke was produced.

X: black smoke is generated.

(production stability)

< evaluation of impregnation State >

Immediately after the SMC production, the carrier film was peeled off with a cutter knife, and the degree of impregnation between the unsaturated polyester resin composition and the glass fiber was visually evaluated.

Regarding the impregnation state, the superiority and inferiority were evaluated according to the following criteria. The results are shown in tables 3 and 4.

O: the glass fibers were sufficiently wetted with the unsaturated polyester resin composition, and no glass fibers were observed which were not impregnated with the unsaturated polyester resin composition.

X: glass fibers not impregnated with the unsaturated polyester resin composition were locally observed.

< evaluation of film Release >

The carrier film of the cured molding material (SMC) was peeled off with a cutter knife, and the film releasability was evaluated.

The film releasability was evaluated for superiority and inferiority according to the following criteria. The results are shown in tables 3 and 4.

O: the SMC had a low tackiness and the film peeled off smoothly.

X: strong tack was observed on the SMC. Or separation of a part of the components was observed upon film peeling.

(Density)

A test piece was cut out from a flat plate-like molded article (thickness: 4mm) used for measurement of molding shrinkage, and the density was measured according to JIS K6911 (1995). The results are shown in tables 3 and 4.

(bending characteristics)

Test pieces (length 80mm, width 10mm) were cut out from flat plate-shaped molded articles (thickness 4mm) used for measurement of molding shrinkage, and flexural strength and flexural modulus were measured at 23 ℃ and 90 ℃ in accordance with JIS K7017 (1999). The results are shown in tables 3 and 4.

From the results of the measurement of flexural modulus and density, the specific stiffness at 23 ℃ and 90 ℃ was calculated by the following formula (1). The results are shown in tables 3 and 4.

Specific stiffness (flexural modulus)^1/3V. Density (1)

(tensile Property)

A test piece was cut out from a flat plate-shaped molded article (thickness: 4mm) used for measurement of the molding shrinkage, and the tensile strength and the tensile elastic modulus were measured at 23 ℃ in accordance with JIS K7164 (2005). The results are shown in tables 3 and 4.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

The present invention is provided as an exemplary embodiment of the present invention, but the present invention is only exemplary and is not to be construed as limiting. Variations of the invention that are obvious to those skilled in the art are intended to be encompassed by the following claims.

Industrial applicability

The unsaturated polyester resin composition, molding material and molded article of the present invention can be suitably used for a battery pack case of an electric vehicle.

The battery pack case for an electric vehicle of the present invention can be suitably used in vehicles requiring low shrinkage, flame retardancy, and dimensional stability.

Description of the reference numerals

1 electric vehicle battery pack case

4 inner side layer

5 outer side layer