JP2021187916A - Polysiloxane copolymer and method for producing the same - Google Patents

Abstract

To provide a copolymer for a low-stress agent which achieves both impartation of flexibility and improvement in adhesiveness when blended into a resin, and to provide a thermosetting resin composition thereof.SOLUTION: The copolymer comprises a siloxane monomer [A], a polyalkylene glycol monomer [B], and an acrylic monomer [C]. The total content derived from the acrylic monomer [C] is less than 40 mass% based on 100 mass% of the copolymer. The copolymer has a functional group content of 0.1-3.0 mmol/g.SELECTED DRAWING: None

Description

The present invention relates to a polysiloxane-based copolymer and a method for producing the same.

Polysiloxane-based polymers exhibit excellent properties such as heat resistance, durability, and flexibility, so they are cosmetics, adhesives, paints, modifiers for electronic materials, mold release agents, and low-stress agents. It is used in a wide range of applications such as. However, the polysiloxane-based polymer has a problem of insufficient adhesiveness to resins and inorganic materials.

Therefore, studies have been conducted on functional improvement in molecular design in which a plurality of monomers are copolymerized. For example, a method of copolymerizing a monomer having a polysiloxane skeleton with a monomer having a polyalkylene glycol skeleton and methyl methacrylate (Patent Document 1), a monomer having a polysiloxane skeleton, a monomer having a polyalkylene glycol skeleton, acrylamide, and the like. And a copolymer of four components of acrylic acid (Patent Document 2) and the like are disclosed.

Japanese Unexamined Patent Publication No. 2005-350369 Japanese Unexamined Patent Publication No. 2017-179121

However, the copolymer described in Patent Document 1 has insufficient intramolecular interaction with the resin, and the copolymer described in Patent Document 2 is intended for cosmetic use.

An object of the present invention is to provide a copolymer for a low stress agent, which imparts flexibility and improves adhesiveness when blended in a resin, and a thermosetting resin composition thereof.

As a result of diligent studies by the present inventors in order to solve the above problems, the following inventions have been reached. The present invention
"<1> The siloxane-based monomer [A] represented by the following general formula (1), the polyalkylene glycol-based monomer [B] represented by the following general formula (2), and the following general formula (3). It is a copolymer composed of an acrylic monomer [C], and the content derived from the acrylic monomer [C] is less than 40% by mass and the functional group content is 0, where the copolymer is 100% by mass. A copolymer characterized by being 1 to 3.0 mmol / g;

In addition, n represents the number of repetition units of 5 to 200. R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents an alkylene group having 1 to 4 ^{carbon atoms, and R 3} represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group.

In addition, m represents the number of repetition units of 3 to 300. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 1 to ^{5 carbon atoms, and R 6} represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Incidentally, X is an oxygen atom or -NR ⁸ - represents, ^{R 7} is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,, ^{R 8} is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, ethyl glycidyl ether group, Represents a propyl glycidyl ether group, a butyl glycidyl ether group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, or a 4-hydroxybutyl group.
<2> The copolymer according to <1>, which has any functional group selected from a carboxyl group, a hydroxyl group, an amide group and an epoxy group.
<3> The copolymer according to <1> or <2>, which has a weight average molecular weight of 5,000 to 500,000.
<4> The monomer [C] is at least one selected from acrylic acid, methacrylic acid, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. The copolymer according to any one of <1> to <3>.
<5> A thermosetting resin composition containing the copolymer according to any one of <1> to <4>. ".

According to the present invention, it is possible to provide a copolymer for a low stress agent, which imparts flexibility and improves adhesiveness when blended in a resin, and an epoxy resin composition thereof.

The copolymer in the present invention is a copolymer composed of a siloxane-based monomer [A], a polyalkylene glycol-based monomer [B], and an acrylic-based monomer [C], and the copolymer is 100% by mass, and the acrylic is described. The system monomer [C] is less than 40% by mass, and the functional group content is 0.1 to 3.0 mmol / g.

The siloxane-based monomer [A] has radical polymerizable properties and is represented by the general formula (1). The monomer imparts the effect of flexibility to the resin, but reduces the adhesiveness.

In addition, n represents the number of repetition units of 5 to 200. The lower limit of n is preferably 7 or more, more preferably 10 or more, and particularly preferably 12 or more. The upper limit of n is preferably 150 or less, more preferably 100 or less, and particularly preferably 70 or less. R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and is preferably a hydrogen atom or a methyl group because of its excellent reactivity. R ² represents an alkylene group having 1 to 4 carbon atoms, and R ² is preferably an ethyl group or a propyl group. R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and may be the same or different from each other. R ³ is preferably a methyl group or a phenyl group, and more preferably a methyl group, because it has an excellent affinity with other units. Specific examples of the siloxane-based monomer [A] include "Silaplane" (registered trademark) FM-0711, FM-0721, FM-0725, which are commercially available from JNC Corporation, and Shin-Etsu Chemical Co., Ltd. Examples thereof include X-22-174ASX, X-22-174BX, KF-2012, X-22-2426, X-22-2404 and the like. The siloxane-based monomer [A] may be used in combination of two or more.

The polyalkylene glycol-based monomer [B] of the present invention has radical polymerizable properties and is represented by the general formula (2). With this monomer, the dispersibility of the copolymer in the resin can be improved, and the flexibility and adhesiveness can be improved.

In addition, R ⁵ represents an alkylene group having 1 to 5 carbon atoms, and may be the same or different from each other. Preferred number of carbon atoms in R ⁵ is 2, 3, or 4. R ⁶ represents a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and is preferably a hydrogen atom or a methyl group because of its excellent affinity with the resin. When R ⁶ is a hydrogen atom, the copolymer has a hydroxyl group. Specific examples of the polyalkylene glycol-based monomer [B] include "New Frontier" (registered trademark) ME-3, ME-4S, MPE-600, and Hitachi Chemical Co., Ltd., which are commercially available from Daiichi Kogyo Seiyaku Co., Ltd. "Funkril" (registered trademark) FA-400M marketed from, "NK ester" (registered trademark) AM-90G, AM-130G, M-90G, M- commercially available from Shin Nakamura Chemical Industry Co., Ltd. Examples thereof include 230G, "light ester" (registered trademark) BC, 130MA, 041MA, and "light acrylate" (registered trademark) MTG-A, 130A, which are commercially available from Kyoeisha Chemical Co., Ltd. The polyalkylene glycol-based monomer [B] may be used in combination of two or more.

m represents the number of repeating units from 3 to 300. As the lower limit of m, 5 or more is preferable, 7 or more is more preferable, and 10 or more is particularly preferable. The upper limit of m is preferably 90 or less, more preferably 80 or less, and particularly preferably 70 or less.

The acrylic monomer [C] of the present invention has radical polymerizable properties and is represented by the general formula (3). The monomer improves the adhesive strength but impairs the flexibility.

Incidentally, X is an oxygen atom or -NR ⁸ - represents a. R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and is preferably a hydrogen atom or a methyl group. R ⁸ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an ethyl glycidyl ether group, a propyl glycidyl ether group, a butyl glycidyl ether group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, or a 4-hydroxybutyl group. , Ethyl group, propyl group, and butyl group are preferable because the molded product of the epoxy resin composition can have a low elastic ratio, and the T _{g of the} copolymer is lowered, so that the epoxy resin containing the copolymer of the present invention is contained. Propyl groups and butyl groups are more preferable because the adhesiveness when the composition is molded on an inorganic material such as glass or metal is improved. When R ⁸ is a hydrogen atom, an ethyl glycidyl ether group, a propyl glycidyl ether group, a butyl glycidyl ether group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, or a 4-hydroxybutyl group, a copolymer. Has a functional group, and the adhesiveness with the resin is improved without impairing the flexibility.

In order to introduce the functional group of the present invention into the copolymer, the acrylic monomer [C] may contain at least acrylic acid, methacrylic acid, acrylamide, methacrylic acid, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate and the like. It contains one or more selected from 2-hydroxyethyl methacrylate. When the functional group content is 0.1 to 3.0 mmol / g, it is possible to achieve both flexibility and adhesive strength. In particular, it was found that by improving the dispersibility of the copolymer in the thermosetting resin, the adhesive strength is significantly improved and the flexibility is compatible, despite the copolymerization of a small amount of the acrylic monomer [C]. rice field. The lower limit of the functional group content is preferably 0.2 mmol / g or more, more preferably 0.3 mmol / g or more, and 0. 4 mmol / g or more is more preferable. Further, when the functional group content is more than 3.0 mmol / g, the flexibility is deteriorated. Therefore, the upper limit of the functional group content is preferably 2.0 mmol / g or less, more preferably 1.5 mmol / g or less. , 1.0 mmol / g or less is more preferable, and 0.8 mmol / g or less is particularly preferable.

The functional group of the copolymer of the present invention is selected from a carboxyl group, a hydroxyl group, an amide group or an epoxy group because the affinity with the thermosetting resin is improved, and even if there are two or more of them. good. Carboxyl groups and epoxy groups are preferable from the viewpoint of improving the adhesiveness with the thermosetting resin, and carboxyl groups are most preferable from the viewpoint of imparting flexibility. Therefore, preferable acrylic monomer [C] is acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate, and particularly acrylic acid and methacrylic acid. These contents can be quantified by known methods. Specifically, when the functional group of the copolymer is a carboxyl group, the copolymer is dissolved in tetrahydrofuran according to JISK0070 and titrated with 0.1 mol / L alcoholic potassium hydroxide using phenolphthalein as an indicator. And calculate. If it is a hydroxyl group, it is quantified by a method according to JISK0070, and if it is an epoxy group, it is quantified by a method according to JISK7236.

Other specific examples of the acrylic monomer [C] include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like. .. Two or more kinds of these acrylic monomers [C] may be used in combination. Butyl acrylate and butyl methacrylate are particularly preferable because they do not impair flexibility.

The copolymer of the present invention has a copolymer content of 100% by mass and a content derived from the acrylic monomer [C] of less than 40% by mass. Even within this range, sufficient adhesive strength can be imparted to the copolymer, and both flexibility and flexibility can be achieved. From the viewpoint of further improving flexibility, it is preferably less than 30% by mass, particularly preferably less than 20% by mass, and even more preferably less than 14% by mass.

Further, in the present invention, the content derived from the siloxane-based monomer [A] is 10 to 90% by mass with the copolymer as 100% by mass. When the content derived from the siloxane-based monomer [A] is less than 10% by mass, the flexibility is lowered, so that the lower limit is preferably 20% by mass or more, more preferably 30% by mass or more. Further, when the content derived from [A] is 90% by mass or more, the adhesiveness is lowered, so that the upper limit of the content derived from [A] is preferably 70% by mass or less, more preferably 60% by mass or less. ..

The weight average molecular weight of the copolymer of the present invention is preferably 5,000 or more and 500,000 or less. When the weight average molecular weight is smaller than 5,000, the toughness of the copolymer is lowered, so that the toughness of the molded product is also lowered. The lower limit of the weight average molecular weight is preferably 5,000 or more, more preferably 7,000 or more, more preferably 10,000 or more, still more preferably 12,000 or more, and particularly preferably 12,000 or more. It is over 15,000. When the weight average molecular weight is larger than 500,000, the viscosity of the copolymer tends to increase and the fluidity tends to deteriorate. Further, when a molded product is obtained from an epoxy resin composition containing a copolymer, it cannot penetrate into the details of the mold at the time of molding, which causes molding defects, which is not preferable. The upper limit of the weight average molecular weight is preferably 500,000 or less, more preferably 100,000 or less, still more preferably 70,000 or less, still more preferably 50,000 or less.

The weight average molecular weight of the copolymer referred to here refers to the weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent and converted into methyl polymethacrylate.

Examples of the method for reacting [A] to [C] include known radical polymerization methods. Radical polymerization can be carried out by using a polymerization initiator that generates radicals in an organic solvent. The polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating, but azo compounds such as azobisisobutyronitrile (AIBN), di-tert-butyl peroxide, tert-butyl hydroperoxide, and peroxides are used. Examples thereof include organic peroxides such as benzoyl and methyl ethyl ketone peroxide. The organic solvent is not particularly limited as long as it dissolves the above [A] to [C], but is an alcohol solvent such as methanol, ethanol, propanol, isopropanol and butanol, toluene, xylene, benzene and 2-methylnaphthalene. Hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, liquid paraffin, ether solvents such as dimethyl ether, diethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl butyl ketone. Ketone solvents such as methyl acetate, ethyl acetate, butyl acetate, butyl propionate, butyl butyrate, ethyl acetoacetate and other ester solvents, chloroform, bromoform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1, Halogenated hydrocarbon solvents such as 1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, 1,1,1,3,3,3-hexafluoroisopropanol, N-methyl-2-pyrrolidone (NMP), Aprotons such as dimethylsulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), propylene carbonate, trimethylphosphate, 1,3-dimethyl-2-imidazolidinone, sulfolane, etc. Examples include sex polar solvents. These organic solvents may be used alone or in admixture of two or more. Further, the solvent can be removed by distillation or a reprecipitation method.

Examples of the terminator and the chain transfer agent include hydroquinone, 1,4-benzoquinone, tert-butylhydroquinone and the like, and the polymerization temperature can be appropriately selected within a known range, and is generally 50 ° C. or higher to 120 ° C. or lower. Is.

The copolymer of the present invention is useful as various additives such as a surfactant and a resin modifier, and among them, it is suitable for a low stress agent of a thermosetting resin. Examples of the thermosetting resin include known resins such as epoxy resin, urethane resin, and melamine resin. In particular, by adding a copolymer to, for example, an epoxy resin, not only the elastic modulus of the epoxy resin composition, which is important for reducing stress, is reduced, but also the adhesiveness with an inorganic material is improved due to its high affinity. Can be done. In particular, when an epoxy resin is selected, its effect is remarkable because it has an excellent affinity with the epoxy group of the epoxy resin and the reactive group of the curing agent.

The epoxy resin composition of the present invention is a mixture of a copolymer and an epoxy resin, a curing agent, and / or a curing accelerator.

The preferable amount of the copolymer contained in the epoxy resin composition of the present invention is 0.1 to 50 parts by mass, preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the epoxy resin. It is more preferably 0.5 to 30 parts by mass, and even more preferably 0.5 to 20 parts by mass. By including the copolymer in this range in the epoxy resin composition, the internal stress can be efficiently relieved in the cured epoxy resin composition obtained by curing the epoxy resin composition.

The epoxy resin is not particularly limited, and for example, a glycidyl ether type epoxy resin obtained from a compound having a hydroxyl group and epichlorohydrin, a glycidylamine type epoxy resin obtained from a compound having an amino group and epichlorohydrin, and the like. A glycidyl ester type epoxy resin obtained from a compound having a carboxyl group and epichlorohydrin, an alicyclic epoxy resin obtained by oxidizing a compound having a double bond, or two or more types of groups selected from these. Epoxy resin or the like mixed in the molecule is used.

Specific examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin obtained by the reaction of bisphenol A and epichlorohydrin, bisphenol F type epoxy resin obtained by the reaction of bisphenol F and epichlorohydrin, 4,4. '-Bisphenol S-type epoxy resin obtained by the reaction of dihydroxydiphenyl sulfone and epichlorohydrin, 4,4'-Biphenyl-type epoxy resin obtained by the reaction of biphenol and epichlorohydrin, resorcinol and epichlorohydrin Resolsinol type epoxy resin obtained by reaction, phenol novolac type epoxy resin obtained by reaction of phenol and epichlorohydrin, other polyethylene glycol type epoxy resin, polypropylene glycol type epoxy resin, and their positional isomers, alkyl groups and halogens. Examples include the substitution product in.

Specific examples of the glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethanes, glycidyl compounds of aminophenol, glycidylanilines, and glycidyl compounds of xylene diamine.

Specific examples of the glycidyl ester type epoxy resin include phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, dimer acid diglycidyl ester, and various isomers thereof.

As the epoxy resin, a resin selected from a biphenyl type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin and a bisphenol S type epoxy resin is preferable from the viewpoint of heat resistance and toughness, and the biphenyl type epoxy resin or bisphenol A is preferable. The type epoxy resin is more preferable, and the biphenyl type epoxy resin is further preferable. The epoxy resin may be used alone or in combination of two or more.

Examples of the curing agent include aliphatic polyamine-based curing agents such as diethylenetriamine and triethylenetetramine; alicyclic polyamine-based curing agents such as mensendiamine and isophoronediamine; aromatic polyamine-based curing agents such as diaminodiphenylmethane and m-phenylenediamine. Acid anhydride-based curing agents such as polyamide, modified polyamines, phthalic anhydride, pyromellitic anhydride and trimellitic anhydride; polyphenol-based curing agents such as phenol novolac resin and phenolaromatic resin; polymercaptan, 2, 4, 6 -Anionic catalysts such as tris (dimethylaminomethyl) phenol, 2-ethyl-4-methylimidazole and 2-phenyl-4-methylimidazole; cationic catalysts such as boron trifluoride-monoethylamine complex; dicyandiamides, aromatics Examples thereof include latent curing agents such as diazonium salts and molecular sieves.

In particular, a curing agent selected from an aromatic amine-based curing agent, an acid anhydride-based curing agent, and a polyphenol-based curing agent is preferably used in terms of providing a cured epoxy resin having excellent mechanical properties.

Specific examples of aromatic amine curing agents include metaphenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, m-xylylenediamine, diphenyl-p-dianiline, various derivatives such as diphenyl-p-dianiline and alkyl substituents thereof, and the position of amino groups. Different isomers can be mentioned.

Specific examples of the acid anhydride-based curing agent include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, hydride methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, and tetrahydrophthalic anhydride. Examples thereof include acid, hexahydrophthalic anhydride, dodecenylphthalic anhydride, benzophenone tetracarboxylic acid dianhydride and the like.

Specific examples of the polyphenol-based curing agent include phenol aralkyl resin, 1-naphthol aralkyl resin, o-cresol novolac epoxy resin, dicyclopentadienephenol resin, terpenephenol resin, naphthol novolak type resin and the like.

The optimum value of the amount of the curing agent added depends on the epoxy resin and the type of the curing agent, but the stoichiometric equivalent ratio of the curing agent is 0.5 with respect to all the epoxy groups contained in the epoxy resin composition. It is preferably between 1 and 1.4, and more preferably between 0.6 and 1.4. When the equivalent ratio is smaller than 0.5, the curing reaction may not occur sufficiently, curing defects may occur, or the curing reaction may take a long time. When the equivalent ratio is larger than 1.4, the curing agent not consumed at the time of curing becomes a defect and may deteriorate the mechanical properties.

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

Examples of the curing accelerator include amine compound-based curing accelerators typified by 1,8-diazabicyclo (5.4.0) undecene-7; imidazoles typified by 2-methylimidazole and 2-ethyl-4-methylimidazole. Compound-based curing accelerator; A phosphorus compound-based curing accelerator typified by triphenylphosphite can be used. Of these, phosphorus compound-based curing accelerators are most preferable.

Various additives such as flame retardants, fillers, colorants, mold release agents and the like may be added to the epoxy resin composition of the present invention, if necessary.

The low stress reducing ability of the copolymer of the present invention can be evaluated by the elastic modulus of the epoxy resin composition, and the higher the low stress reducing ability, the lower the elastic modulus as compared with the case where the copolymer is not used. do. The elastic modulus is evaluated by a method according to JIS K7171 (2008).

The epoxy resin composition of the present invention exhibits excellent adhesiveness by being applied to an inorganic material and then cured. The adhesiveness can be evaluated by a method according to JIS K6850.

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

(1) Quantification of functional group content When the copolymer has a carboxyl group, 0.5 g of the block copolymer is dissolved in 10 g of tetrahydrofuran, and phenolphthalein is mixed with 0.1 mol / L alcoholic potassium hydroxide. It was titrated as an indicator and the carboxyl group content was quantified. When it contained a hydroxyl group, it was quantified by a method according to JISK0070. When it had an epoxy group, it was quantified by a method according to JISK7236.

(2) Measurement of weight average molecular weight The weight average molecular weight of the copolymer was measured under the following conditions using a gel permeation chromatography method, and the molecular weight was calculated using a calibration curve with polymethyl methacrylate.
Equipment: Shimadzu Corporation LC-20AD Series Column: Showa Denko Corporation KF-806L x 2
Flow rate: 1.0 mL / min
Mobile phase: Tetrahydrofuran Detection: Differential refractometer Column temperature: 40 ° C

(3) Evaluation of flexural modulus The evaluation was made by a method according to JIS K7171 (2008).

(4) Evaluation of Adhesiveness Evaluation was made by a method according to JISK6850 (1999).

[Manufacturing Example 1]
50 g (50 mmol) of a siloxane-based monomer [A] (manufactured by JNC Co., Ltd., "Silaplane" (registered trademark) FM-0711) and a polyalkylene glycol-based monomer [B] ("" 35 g (24.6 mmol) of "light ester" (registered trademark) 041MA), 5 g (69.4 mmol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) as an acrylic monomer [C] and butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) ), 0.5 g (3.0 mmol) of azoisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization initiator, and 50 g of isopropanol (manufactured by Tokyo Chemical Industry Co., Ltd.) as an organic solvent. , Nitrogen substitution was performed. Then, it reacted at 80 degreeC for 8 hours and cooled to room temperature. The organic solvent was completely removed by an evaporator and a vacuum dryer at 80 ° C. to obtain a copolymer. The content derived from [A] is 50% by mass, the content derived from [B] is 35% by mass, the content derived from [C] is 15% by mass, and the functional group content (carboxyl group) is 0.70 mmol. / G, weight average molecular weight was 58,000. The results are shown in Table 1.

[Manufacturing Example 2]
Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 5 g (69.4 mmol), 4-hydroxybutyl acrylate glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 13 g (65.0 mmol), butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 10 g (78.1 mmol) was changed to 2 g (15.6 mmol), and a copolymer was obtained in the same manner as in Production Example 1. The content derived from [A] is 50% by mass, the content derived from [B] is 35% by mass, the content derived from [C] is 15% by mass, and the functional group content (epoxide group) is 0.66 mmol. / G, weight average molecular weight was 50,000. The results are shown in Table 1.

[Manufacturing Example 3]
Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 5 g (69.4 mmol), 4-hydroxybutyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 g (69.4 mmol), butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) A copolymer was obtained in the same manner as in Production Example 1 except that 10 g (78.1 mmol) was changed to 5 g (39.1 mmol). The content derived from [A] is 50% by mass, the content derived from [B] is 35% by mass, the content derived from [C] is 15% by mass, and the functional group content (hydroxyl group) is 0.68 mmol /. The weight average molecular weight was 55,000. The results are shown in Table 1.

[Reference Example 1]
In a glass reaction vessel with a cooling tube installed, 50 g (50 mmol) of "Silaplane" (registered trademark) FM-0711 (manufactured by JNC Co., Ltd.) as a siloxane-based monomer [A] and "polyalkylene glycol-based monomer [B] as" 35 g (24.6 mmol) of "Light Ester" (registered trademark) 041MA (manufactured by Kyoeisha Chemical Co., Ltd.), 15 g (117 mmol) of butyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as an acrylic monomer [C], a polymerization initiator. As a result, 0.5 g (3.0 mmol) of azoisobutyronitrile (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 50 g of isopropanol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as an organic solvent were added and subjected to nitrogen substitution. Then, it reacted at 80 degreeC for 8 hours and cooled to room temperature. The organic solvent was completely removed by an evaporator and a vacuum dryer at 80 ° C. to obtain a copolymer. The content derived from [A] is 50% by mass, the content derived from [B] is 35% by mass, the content derived from [C] is 15% by mass, the functional group content is 0 mmol / g, and the weight average molecular weight. Was 48,000. The results are shown in Table 1.

[Reference Example 2]
In a glass reaction vessel with a cooling tube installed, 50 g (50 mmol) of "Silaplane" (registered trademark) FM-0711 (manufactured by JNC Co., Ltd.) as a siloxane-based monomer [A] and "polyalkylene glycol-based monomer [B] as" 5 g (3.5 mmol) of "light ester" (registered trademark) 041MA (manufactured by Kyoeisha Chemical Co., Ltd.), 25 g (347 mmol) of acrylic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as an acrylic monomer [C] and butyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 20 g (156 mmol) of Tokyo Kasei Kogyo Co., Ltd., 0.5 g (3.0 mmol) of azoisobutyronitrile (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a polymerization initiator, and isopropanol (Tokyo Kasei Kogyo Co., Ltd.) as an organic solvent. 50 g (manufactured by the company) was added and nitrogen substitution was performed. Then, it reacted at 80 degreeC for 8 hours and cooled to room temperature. The organic solvent was completely removed by an evaporator and a vacuum dryer at 80 ° C. to obtain a copolymer. The content derived from [A] is 50% by mass, the content derived from [B] is 5% by mass, the content derived from [C] is 45% by mass, and the functional group content (carboxyl group) is 3.5 mmol. The weight average molecular weight was 59000 at / g. The results are shown in Table 1.

[Examples 1 to 3 and Comparative Examples 1 to 3]
9.0 g of the copolymers obtained in Production Examples 1 to 2 and Reference Examples 1 to 2, 30 g of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., "jER" (registered trademark) 828) as an epoxy resin, cured. As an agent, 30 g of "Epoxy" (registered trademark) MH-700 (manufactured by Shin Nihon Rika Co., Ltd.) and 0.45 g of 4-methyl2-phenylimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a curing accelerator are 150 cc of stainless steel. Weigh it in a beaker, mix it easily with a stirring rod, and then use a self-rotating mixer "Awatori Rentaro" (manufactured by Shinky Co., Ltd.) to mix at 2000 rpm, 80 kPa, and 1.5 minutes once at 2000 rpm. Stirring at 50 kPa for 1.5 minutes was performed once, and stirring at 2000 rpm at 0.2 kPa for 1.5 minutes was performed twice to obtain an uncured epoxy resin composition.

This uncured epoxy resin composition was cast into an aluminum mold set with a 4 mm thick "Teflon" (registered trademark) spacer and a release film, and placed in an oven. The temperature of the oven was set to 80 ° C., and after holding for 5 minutes, the temperature was raised to 150 ° C. at a heating rate of 1.5 ° C./min and cured for 2 hours to obtain a cured epoxy resin having a thickness of 4 mm.

The obtained cured epoxy resin was cut into a width of 10 mm and a length of 80 mm, and three points were obtained according to JIS K7171 (2008) using a Tensilon universal tester (TENSILON TRG-1250, manufactured by A & D Co., Ltd.). A bending test was performed. For the adhesive strength, the above-mentioned uncured epoxy resin composition was applied to a thickness of 5 μm, the glass substrates were bonded, and the mixture was placed in an oven. The temperature of the oven was set to 80 ° C., and after holding for 5 minutes, the temperature was raised to 150 ° C. at a heating rate of 1.5 ° C./min, and the mixture was cured for 2 hours. The obtained cured product was measured for adhesive strength with a glass plate using a multi-bond tester (SS-30WD, manufactured by Seishin Shoji Co., Ltd.) according to JISK6850 (1999). The results are shown in Table 2.

The copolymer of the present invention is useful as various additives such as surfactants and resin modifiers, and its application to cosmetics, adhesives, paints, electronic material applications and the like is described. In particular, it is suitably used for low stress agents for resins.

Claims (5)

The siloxane-based monomer [A] represented by the following general formula (1), the polyalkylene glycol-based monomer [B] represented by the following general formula (2), and the acrylic monomer represented by the following general formula (3). A copolymer composed of [C], wherein the copolymer is 100% by mass, the content derived from the acrylic monomer [C] is less than 40% by mass, and the functional group content is 0.1 to 3. A copolymer characterized by being 0.0 mmol / g;

In addition, n represents the number of repetition units of 5 to 200. R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents an alkylene group having 1 to 4 ^{carbon atoms, and R 3} represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group.

In addition, m represents the number of repetition units of 3 to 300. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 1 to ^{5 carbon atoms, and R 6} represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Incidentally, X is an oxygen atom or -NR ⁸ - represents, ^{R 7} is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,, ^{R 8} is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, ethyl glycidyl ether group, Represents a propyl glycidyl ether group, a butyl glycidyl ether group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, or a 4-hydroxybutyl group. The copolymer according to claim 1, which has any functional group selected from a carboxyl group, a hydroxyl group, an amide group and an epoxy group. The copolymer according to claim 1 or 2, wherein the weight average molecular weight is 5,000 to 500,000. Claimed that the monomer [C] is at least one selected from acrylic acid, methacrylic acid, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. Item 3. The copolymer according to any one of Items 1 to 3. A thermosetting resin composition comprising the copolymer according to any one of claims 1 to 4.