TWI585158B - Curable resin composition - Google Patents

Description

Curable resin composition

The present invention relates to a curable resin composition which is capable of obtaining a cured film excellent in adhesion to a substrate and flexibility even in a cold region.

Conventionally, in order to improve the adhesion to an inorganic substrate such as a coating material containing an epoxy resin as a main component, there is a technique of adding a decane coupling agent (for example, Patent Document 1). However, most of the decane coupling agents have a low boiling point and require a large amount of addition to the thermosetting resin. Further, the effect of improving the adhesion by the addition of the decane coupling agent cannot be said to be sufficient. For example, it is possible to achieve practical use by simultaneously adding a salt such as a salt such as titanium or zirconium, a phosphate ester or a urethane resin. The level of attachment required in the standard is also high. In this case, the addition of these adhesion aids not only increases the number of processes, but also requires the selection of an adhesion aid which does not impair the coating properties, and the strict optimization operation of the amount of addition.

Therefore, Patent Document 2 proposes a curable resin composition which has a polyfunctional thiol compound, a specific thioether alkoxydecane derivative and an epoxy resin composition, and a plurality of double bonds. The functional polyene is mixed. In the curable resin composition, it is not necessary to add another adhesion aid or the like as in the case of using a decane coupling agent, that is, it can exhibit excellent adhesion to an inorganic substrate.

Prior art document [Patent Document]

Patent Document 1: Japanese Patent Publication No. 7-300491

Patent Document 2: JP-A-2012-246464

[Problems to be solved by the invention]

However, it has been known that, as disclosed in Patent Document 2, a polyfunctional thiol compound, a specific thioether-containing alkoxydecane derivative, and an epoxy resin composition and a polyfunctional polyene having a plurality of double bonds are mixed and cured. The resin composition is excellent in adhesion to an inorganic substrate and excellent in storage stability of the resin composition. However, since the cured film lacks flexibility in a cold region, cracks are likely to occur when the cured film is bent. Further, there is a technical problem of lack of attachment.

The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a material which is excellent in adhesion to a substrate even in a cold region, and which has a softened cured film.

[Technical means to solve technical problems]

In order to solve the above-described problems, the curable resin composition of the present invention contains (A) a sulfide-containing (meth) acrylate derivative represented by the following formula 1, and (B) a polyfunctional weight having a weight average molecular weight of 200 to 50,000 ( Methyl) acrylate, the mass ratio of (A) component to (B) component ((A)/(B)) is 0.05 to 30,

Where a is an integer from 1 to 5, b is an integer from 0 to 2, c is an integer from 1 to 5, a sum of b and c is 6; and R ¹ is a methylene group, an ethylene group or a hetero-Asia a propyl group; R ² is a divalent functional group represented by the following formula 2 or the following formula 3; R ³ is a methyl group or an ethyl group; R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms; and R ⁶ is represented by the following formula 4; a hexavalent functional group, R ⁵ is a hydrogen atom or a methyl group, R ⁵ is a hydrogen atom or a methyl group, .

Further, in the present invention, the molecular weight is a weight average molecular weight unless otherwise specified.

The curable resin composition of the present invention may further contain (C) a photopolymerization initiator in addition to the components (A) to (B). 0.01 to 10 parts by mass of the component (C) is added to 100 parts by mass of the total mass of the component (A) and the component (B).

The curable resin composition of the present invention may further contain (D) an amine compound having a weight average molecular weight of 90 to 700 in addition to the components (A) to (B) or (A) to (C). 0.01 to 50 parts by mass of the component (D) is added to 100 parts by mass of the total mass of the component (A) and the component (B).

Further, in the present invention, "(meth) acrylate" is a generic term including both acrylate and methacrylate. Similarly, "(meth)acryloxy" is a generic term for both propylene methoxy and methacryloxy, and "(meth)acrylic acid" is a generic term for both acrylic acid and methacrylic acid. . Further, unless otherwise stated, "○○~××" indicating a numerical range in the present invention is a concept including a lower limit value ("○○") and an upper limit value ("××"). That is, the correct meaning is "○○ or more × × or less".

[effect of the invention]

According to the curable resin composition of the present invention, the specific thioether-containing (meth) acrylate derivative (A) can be added as a specific component having a specific molecular weight in a balanced manner as an active component for improving the adhesion action. (Meth) acrylate (B). Thereby, it is possible to achieve excellent adhesion to the substrate without adding another adhesion aid or the like as in the case of using a decane coupling agent. In particular, even in a cold region, the obtained cured film exhibits excellent adhesion to a substrate and flexibility.

The invention is described in detail below. The curable resin composition of the present invention is a curable resin composition containing at least one of the components (C) and (D) as an essential component, and further containing the following components (A) and (B).

<Sulfur ether (meth) acrylate derivative ((A) component)>

The thioether-containing (meth) acrylate derivative as the component (A) is a compound represented by the following formula 1.

Where a is an integer from 1 to 5, b is an integer from 0 to 2, c is an integer from 1 to 5, a sum of b and c is 6; and R ¹ is a methylene group, an ethylene group or a hetero-Asia a propyl group; R ² is a divalent functional group represented by the following formula 2 or the following formula 3; R ³ is a methyl group or an ethyl group; R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms; and R ⁶ is represented by the following formula 4; a hexavalent functional group, R ⁵ is a hydrogen atom or a methyl group, R ⁵ is a hydrogen atom or a methyl group, .

Examples of the hydrocarbon group having 1 to 12 carbon atoms of R ⁴ in the above formula 1 include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group. In the above formula R ¹¹ identical to each other methylene, ethylene, or isopropylidene, the increase in terms of the effect of improving the adhesion, particularly preferably ethylene, isopropylidene.

<Polyfunctional (meth) acrylate ((B) component)>

The polyfunctional (meth) acrylate as the component (B) has a (meth) acryloxy group at the terminal, and a preferred example thereof is a compound represented by the following formula 5. Further, the polyfunctional (meth) acrylate as the component (B) may be used alone or in combination of two or more.

In the formula, d is an integer of 2 to 30, R ⁷ is a hydrocarbon group having 2 to 200 carbon atoms, a group having 2 to 300 carbon atoms and consisting only of an etheroxy group (-O-) and a hydrocarbon group, or only A group consisting of an isocyanurate ring or an isocyanurate ring and a hydrocarbon group, and R ⁸ is a hydrogen atom or a methyl group.

Further, as the (B) polyfunctional (meth) acrylate, a polymer type polyfunctional (meth) acrylate is also suitably used. Examples of the polymer type polyfunctional (meth) acrylate include (meth) acrylate and (meth) acrylate glycidol which have a group reactive with an epoxy group, for example, (meth)acrylic acid. a polymer obtained by reacting an epoxy group-containing (meth) acrylate monomer or copolymer such as an ester; and a group having a reaction with a hydroxyl group such as 2-isocyanoethyl 2-methacrylate a polymer obtained by reacting a (meth) acrylate monomer or a copolymer having a hydroxyl group such as (meth) acrylate with hydroxyethyl (meth) acrylate; for example, glycidyl (meth)acrylate A polymer obtained by reacting a (meth) acrylate having a group reactive with a carboxyl group with a (meth) acrylate monomer or copolymer having a carboxyl group such as (meth)acrylic acid.

(B) The polyfunctional (meth) acrylate has a weight average molecular weight of 200 to 50,000. (B) When the weight average molecular weight of the polyfunctional (meth) acrylate is less than 200, there is no problem in adhesion, but the volatility tends to be high and the odor tends to be strong, which is not preferable. On the other hand, when the weight average molecular weight is more than 50,000, there is no problem in adhesion, but there is a possibility that solubility in other components is lowered, which is not preferable.

Further, the (meth) acrylate equivalent of the (B) polyfunctional (meth) acrylate is from 80 to 6000 g/mol. If the (meth) acrylate equivalent is less than 80 g/mol, the (meth) propylene oxime group per unit volume becomes excessive, and the thiol group of the (A) thioether (meth) acrylate derivative is not Since the (meth) propylene oxime group of the reaction remains in a large amount, the toughness of the cured film formed of the curable resin composition may be lowered, and the adhesion may be lowered. On the other hand, if the (meth) acrylate equivalent is more than 6000 g/mol, the thiol group of the (A) thioether-containing (meth) acrylate derivative is remarkably lowered due to a significant decrease in the (meth) propylene oxime group concentration. Since the reaction efficiency is lowered, the toughness of the cured film formed of the curable resin composition is lowered, and the adhesion is lowered.

<Photopolymerization initiator ((C) component)>

The photopolymerization initiator as the component (C) is added to promote the reaction between the thiol group and the (meth) propylene decyloxy group, and it is possible to reduce the light irradiation required for curing of the curable resin composition. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, a photoanion polymerization initiator, and the like. The photoradical polymerization initiator is preferably used in the case of shortening the reaction time, and the photocationic polymerization initiator is preferably used in the case of reducing the curing shrinkage, and the photoanionic polymerization initiator is preferably imparted in the field of electronic circuits and the like. Used when bonding.

Examples of the photoradical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, and 2- Hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1 -ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]-phenyl}-2-methyl-propan-1-one, 2 -methyl-1-[4-(methylthio)phenyl]-2-morpholinan-1-one, bis(2,4,6-trimethylbenzhydrazide)-phenylphosphine oxide, 2 , 4,6-trimethylbenzhydrazide-diphenyl-phosphine oxide, and the like.

Examples of the photocationic polymerization initiator include bis(4-t-butylphenyl)iodonium hexafluorophosphate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, and cyclopropane. Diphenylphosphonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, 2-(3,4-dimethoxystyryl)-4,6 - bis(trichloromethyl)-1,3,5-triazine, triphenylsulfonium tetrafluoroborate, triphenylphosphonium bromide, tri-p-tolylphosphonium hexafluorophosphate, tri-p-tolyl Trifluoromethanesulfonate and the like.

Examples of the photoanionic polymerization initiator include acetophenone o-benzidine, nifedipine, and 2-(9-oxobenzophenone-2-yl)propionic acid 1,5,7-trinitrogen. Heterobicyclo[4,4,0]non-5-ene, 2-nitrophenylmethyl 4-methylpropenyloxy acridine-1-carboxylate, 1,2-diisopropyl- 3-[Bis(dimethylamino)methylene]indole 2-(3-benzhydrylphenyl)propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanide Butyl triphenyl borate and the like.

<Amine compound ((D) component)>

The amine compound as the component (D) is used to promote (catalyze) the reaction of a thiol group with a (meth) propylene decyloxy group. More specifically, by containing the component (D), the thiol group and the (meth) acryloxy group can be reacted at a low temperature, so that the curable resin containing the component (A) and the component (B) can be combined. The material is cured at a low temperature. The amine compound as the component (D) may, for example, be a monofunctional amine having a weight average molecular weight of 90 to 700 or a polyamine having a plurality of amino groups. When the weight average molecular weight of the amine compound is less than 90, the volatility of the amine becomes high, which causes not only odor or voids, but also the amine concentration at the time of heat curing becomes low, and the crosslinking reaction becomes difficult to carry out, and the adhesion is easy. reduce.

When the weight average molecular weight of the amine compound exceeds 700, the water resistance is lowered, and the adhesion is liable to lower.

The monofunctional amine may, for example, be a primary amine, a secondary amine or a tertiary amine. Examples of the polyamine include a primary amine, a secondary amine, a tertiary amine, and a complex amine. The complex amine means an amine having two or more kinds of a primary amino group, a secondary amino group, and a tertiary amino group. Examples of such a complex amine include an imidazoline compound, an imidazole compound, an N-substituted pyridazine compound, and an N,N-dimethylurea derivative. Further, the amine compounds may be used alone or in combination of two or more.

Further, in order to adjust the catalytic activity, the amine compound may be previously formed as a salt with an organic acid. Examples of the organic acid to be reacted with the amine compound in advance include an aliphatic carboxylic acid having 1 to 20 carbon atoms and having 1 to 5 carboxyl groups in the molecule, 7 to 20 carbon atoms, and 1 to 10 carboxyl groups in the molecule. Aromatic carboxylic acid or isocyanuric acid.

Among the amine compounds, the highly basic imidazole compound is suitably cured at the lowest temperature. Further, a coated imidazole compound such as a phenol resin or the like can be used.

This imidazole compound is a compound represented by the following formula 6.

R ¹⁰ is a cyano group, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with 2,3-diaminotriazine, an alkoxy group having 1 to 4 carbon atoms or a hydrogen atom, and R ⁹ R ¹¹ and R ¹² are a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydrogen atom, and when the ring is a ring of R ⁹ to R ^{12 , the} number of carbon atoms is 2 to 8. Hydrocarbyl group.

Specific examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, and 2-phenyl-4. -methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2- Methylimidazole, 1-(2-cyanoethyl)-2-undecylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 1-(2-cyanoethylidene) 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole 2,4-Diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl- (1')]-Ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-three Pyrazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole.

<composition ratio (add balance)>

The curable resin composition of the present invention has a mass ratio ((A)/(B)) of (A) a sulfide-containing (meth) acrylate derivative to (B) a polyfunctional (meth) acrylate of 0.05. Add ~30 way. Here, "(A)/(B)" means the value of (A) the mass of the thioether (meth) acrylate derivative divided by the mass of (B) polyfunctional (meth) acrylate. When (A)/(B) is less than 0.05 or exceeds 30, there is a tendency that the adhesion is lowered. The optimum (A)/(B) value depends on the characteristics of the curable resin composition required, (A) the thioether (meth) acrylate derivative and (B) the polyfunctional (meth) acrylate type. different. The properties after curing the curable resin composition are strictly controlled by the number of (thiol groups)/((meth)acryloxy group) per unit weight of the curable resin composition (hereinafter referred to as thiol/ene ratio) The impact of the value. For example, when the thiol/olefin ratio is in the range of 0.5 to 1.5, dense crosslinking is likely to occur, and it is likely to be a tough cured product. On the other hand, when the thiol/ene ratio is 0.1 or more and less than 0.5, or more than 1.5 and 2.0 or less, a soft and viscous cured product can be obtained. When the thiol/ene ratio is less than 0.1 or exceeds 2.0, gelation becomes difficult, and the adhesion tends to be lowered.

Further, in the case where (C) a photopolymerization initiator is added to the curable resin composition of the present invention, it is relative to (A) a sulfide-containing (meth) acrylate derivative and (B) a polyfunctional (meth) group. 100 parts by mass of the total mass of the acrylate ((A) + (B))) is added so that the (C) photopolymerization initiator is 0.01 to 10 parts by mass. When the amount of the component (C) added is less than 0.01 parts by mass based on 100 parts by mass of ((A) + (B)), a large amount of accumulated light amount is required to carry out the reaction of the thiol group with the (meth) acryloxy group. When it exceeds 10 parts by mass, the crosslinking density may be lowered, and the adhesion may be lowered.

Further, in the case where the (D) amine compound is added to the curable resin composition of the present invention, it is relative to (A) a sulfide-containing (meth) acrylate derivative and (B) a polyfunctional (meth) acrylate. 100 parts by mass of the total mass ((A) + (B))) is added so that the (D) amine compound is 0.01 to 50 parts by mass. When the amount of the component (D) is less than 0.01 with respect to 100 parts by mass of ((A) + (B)), the function as a catalyst is insufficient, and curing cannot be promoted by heating, and if it exceeds 50 parts by mass, the curable resin The storage stability of the composition is lowered.

<Formation of cured film>

The curable resin composition of the present invention can be formed into a cured film by coating and curing on a substrate. The curable resin composition of the present invention exhibits adhesion to a substrate by (A) a thioether group of a sulfide-containing (meth) acrylate derivative. Therefore, the substrate is excellent in adhesion improving effect to a substrate having a chemical bond (high chemical affinity) with a thioether group, and for example, an inorganic group such as a transition metal or an alloy thereof, a ruthenium compound, a phosphorus compound, a sulfur compound or a fluorine compound. An organic substrate having an unsaturated bond (including an aromatic ring), an organic substance having a hydroxyl group or a carboxyl group, or an organic substance treated by plasma or UV ozone. Specifically, examples of the inorganic substrate include glass, enamel, various metals, and the like. Examples of the organic substrate include a poly(meth)acrylic resin, a cellulose triacetate (TAC) resin, polyethylene terephthalate (PET), and polybutylene terephthalate. Polyester resin, polycarbonate resin, polyimide resin, polyolefin resin such as polyethylene or polypropylene, polycarbonate, polyimine, ABS resin, polyvinyl alcohol, vinyl chloride resin , polyacetal, and the like. Further, the curable resin composition of the present invention has a specific hydrocarbon group by the (A) thioether-containing (meth) acrylate derivative, and the cured film is excellent in flexibility. Therefore, in a cold condition, the cured film easily follows the substrate and is excellent in adhesion to the substrate. Therefore, it is especially suitable for the coating of flexible substrates which can be used under cold conditions.

The curable resin composition can be cured by irradiation with light, and examples of the light to be irradiated include an active energy ray such as UV (ultraviolet light) or EB (electron beam). In addition, when the curable resin composition comprising component (C) can be generally desirable to reduce to 100mJ / cm ² irradiation amount of light around about 2500mJ / cm ^2. Further, when the curable resin composition contains the component (D), it may be cured at a low temperature of about 80 ° C or may be cured by a two-stage process of a light-curing curing process and a heated curing process.

In order to make the reaction system uniform and easy to apply, the curable resin composition of the present invention can also be used by being diluted with an organic solvent. Examples of such an organic solvent include an alcohol solvent, an aromatic hydrocarbon solvent, an ether solvent, an ester solvent, an ether ester solvent, a ketone solvent, and a phosphate solvent. The organic solvent is preferably controlled to be added in an amount of less than 10,000 parts by mass based on 100 parts by mass of the curable resin composition. Basically, the solvent volatilizes when the cured film is formed, so that the physical properties of the cured film are not greatly affected. .

Further, for the purpose of adjusting the viscosity, the curable resin composition of the present invention may be added with a viscosity adjusting agent such as cerium oxide powder. These viscosity modifiers are preferably controlled to be added in an amount of less than 300 parts by mass based on 100 parts by mass of the curable resin composition. When the amount of the viscosity modifier added exceeds 300 parts by mass, the adhesion may be lowered.

Further, the curable resin composition of the present invention may be added with various additives for use in a usual paint or adhesive. Examples of such an additive include a surfactant for smoothing the coated surface, and an aluminum salt for extending the usable time. The additive is preferably controlled to be added in an amount of less than 80 parts by mass based on 100 parts by mass of the curable resin composition. When the amount of the additive added exceeds 80 parts by mass, there is a possibility that the adhesion is lowered. Example

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited thereto. The components used in the examples and comparative examples are as follows. Further, Mw represents a weight average molecular weight.

<(A) component>

(A-1: thioether (meth) acrylate derivative)

(A-2: thioether (meth) acrylate derivative)

(A-3: thioether (meth) acrylate derivative)

(A-4: thioether (meth) acrylate derivative)

(A'-5: polythiol compound)

(A'-6: polythiol compound)

(A'-7: thioether alkoxydecane derivative)

(A'-8: thioether alkoxydecane derivative)

(A'-9: thioether (meth) acrylate derivative)

<(B) component: polyfunctional (meth) acrylate>

(B-1, Mw: 5000) n is an average of 13.

(B-2, Mw: 246)

(B-3, Mw: 352)

(B-4, Mw: 22000) A polymer obtained by adding a molar methacrylic acid to a copolymer of glycidyl methacrylate and cyclohexyl methacrylate using D-3 as a catalyst (using B-3) A white solid obtained by reprecipitation of a 50 wt% methyl isobutyl ketone solution.

(B-5, Mw: 45000) A polymer obtained by adding a molar methacrylic acid to a copolymer of glycidyl methacrylate and cyclohexyl methacrylate using D-3 as a catalyst (using B-3) A white solid obtained by reprecipitation of a 50 wt% methyl isobutyl ketone solution.

<(C) component: photopolymerization initiator>

(C-1, Mw: 204) 1-hydroxy-cyclohexyl-phenyl-one

(C-2, Mw: 348) 2,4,6-trimethylbenzhydrazide-diphenyl-phosphine oxide

(C-3, Mw: 407) 2-(9-oxobenzophenone-2-yl)propionic acid 1,5,7-triazabicyclo[4.4.0]non-5-ene

<(D) component: amine compound>

(D-1, Mw: 110)

(D-2, Mw: 102) N,N-dimethyl-1,3-propanediamine

(D-3, Mw: 680) N1, n2, and n3 are integers of 1 to 5, and an average of 3.5 mixtures.

The components (A) to (D) were mixed with the addition ratios shown in Tables 1 to 4, and the mixture was stirred until uniform with a spatula to obtain samples of the curable resin compositions of the examples and the comparative examples. The samples of the curable resin compositions of the obtained examples and the comparative examples were subjected to the following adhesion 1 (room temperature adhesion), adhesion 2 (cold area adhesion), flexibility, and storage stability. Sexual evaluation. The results are shown in Tables 1 to 4.

[Production of test piece for evaluation]

The test pieces for adhesion 1, adhesion 2, and softness evaluation were obtained in the following manner. Each sample of the curable resin composition was applied to a thickness of 100 μm on a 25 mm wide PET film by a die coater, and another PET film was superposed thereon to obtain curing conditions shown in Tables 1 to 4. A test piece for evaluation of curing. Further, Lumirror U46-100 manufactured by Toray Industries, Inc. was used as the PET film. For the light irradiation, the light lamp system "Light hammer 6" manufactured by Heraeus Noblelight Fusion UV Co., Ltd. was used, and the bulb was an H bulb.

[Adhesiveness 1 (room temperature attachment)]

The test piece for evaluation was allowed to stand at 25 ° C for 24 hours, and then measured by a T-peel method defined by JIS K6854-3, and evaluated as follows.

◎: Tensile strength is 5N/25mm or more (PET film fracture)

○: Tensile strength is 5 N/25 mm or more (PET film is not broken)

×: less than 5N/25mm

[Attach 2 (cold area attachment)]

The test piece for evaluation was allowed to stand at -10 ° C for 24 hours, and then measured by a T-peel method defined by JIS K6854-3, and evaluated as follows.

◎: Tensile strength is 5N/25mm or more (PET film fracture)

○: Tensile strength is 5 N/25 mm or more (PET film is not broken)

×: less than 5N/25mm

[softness]

The test piece for evaluation was allowed to stand at -10 ° C for 24 hours, and then wound up on a rod having a diameter of 8 mm for 1 minute, visually observed, and evaluated in the following manner.

○: no cracks

×: cracked

[save stability]

The sample of the curable resin composition of each of the examples and the comparative examples was measured for viscosity at 25° C. (viscosity immediately after mixing) immediately after mixing, and then heated at 40° C. for 12 hours, and then the viscosity was measured again (viscosity after heating). The viscosity after heating was divided by the viscosity immediately after mixing, and the thickening ratio was calculated and evaluated as follows. In addition, the viscosity was measured by the following conditions using an R-type viscometer manufactured by Toki Sangyo Co., Ltd.

Use rotor: 1°34′×R24

Measuring range: 0.5183~103.7 Pa•s

◎: Thickening rate 1.0~1.8

○: Thickening rate 1.8~10

×: the thickening rate is outside the above range

[Table 1]

[Table 2]

[table 3]

[Table 4]

The curable resin composition of Examples 1-1 to 1-12 was able to confirm high adhesion, good flexibility, and excellent storage stability at room temperature and cold conditions. The curable resin compositions of Examples 2-1 to 2-5 were cured by a small amount of light irradiation, and high adhesion, good flexibility, and excellent storage stability were confirmed under room temperature and cold conditions. The curable resin compositions of Examples 3-1 to 3-6 were cured by a small amount of light irradiation and low-temperature heating, and high adhesion, good flexibility, and excellent storage stability were confirmed under room temperature and cold conditions. Sex. The curable resin composition of Example 3-7 was cured by low-temperature heating, and exhibited high adhesion and good flexibility at room temperature and cold conditions. On the other hand, in Comparative Example 1-1 in which the component (A) was too small relative to the component (B) and the component (B) in which the component (A) was excessive in relation to the component (B), not only the cold temperature but also the temperature at room temperature was attached. The attachment is also poor. In Comparative Examples 1-3 to 1-7 in which the compound having the structure of the above formula 1 was used as the component (A), the adhesion under cold conditions was poor.

no.

no.

no.

Claims (3)

A curable resin composition comprising (A) a sulfide-containing (meth) acrylate derivative represented by the following formula 1, and (B) a polyfunctional (meth) acrylate having a weight average molecular weight of 200 to 50,000. The mass ratio (A)/(B) of the component (A) to the component (B) is 0.05 to 30, In the formula, a is an integer of 1 to 5, b is an integer of 0 to 2, c is an integer of 1 to 5, a sum of b and c is 6; and R ¹ is a methylene, sub Ethyl or isopropylidene; R ² is a divalent functional group represented by the following formula 2 or the following formula 3; R ³ is a methyl group or an ethyl group; and R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms; R ⁶ is a hexavalent functional group represented by the following formula 4, R ⁵ is a hydrogen atom or a methyl group. R ⁵ is a hydrogen atom or a methyl group. . The curable resin composition according to the first aspect of the invention, wherein the (C) light is further added in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total mass of the component (A) and the component (B). Polymerization initiator. The curable resin composition according to claim 1 or 2, wherein the amount of the component (A) and the component (B) is further added in an amount of 0.01 to 50 parts by mass based on 100 parts by mass of the total mass of the component (B). An amine compound having a weight average molecular weight of 90 to 700.