Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/061—Polyesters; Polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
  • C08F291/02—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to elastomers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

• the present invention relates to a composition.
• the present invention relates to a composition which exhibits excellent flexibility, heat cycle resistance and heat resistance, and exhibits excellent adhesion to both metals and resins.
• a room temperature fast-curing adhesive composition is used as an adhesive that adheres in a short time at room temperature.
• the room temperature fast-curing adhesive composition include a two-part fast-curing epoxy adhesive composition, an anaerobic adhesive composition, an instant adhesive composition, and a second-generation acrylic adhesive composition (SGA).
• SGA second-generation acrylic adhesive composition
• the two-part type fast-curing epoxy adhesive measures and mixes the main agent and the curing agent, applies them to the adherend, and cures by the reaction between the main agent and the curing agent.
• Two-part fast-curing epoxy adhesives have generally been widely used as structural adhesives because of their high durability and high adhesive strength.
• the conventional two-part fast-curing epoxy adhesive has a hard and brittle surface, and its flexibility is extremely low. Therefore, when it is used for bonding different types of adherends, it is not possible to alleviate the strain caused by the difference in linear expansion coefficient between different adherends, and peeling and cracks often occur. Further, if the main agent and the curing agent are not accurately weighed so as to have a predetermined mixing ratio, there is a problem that curing failure occurs.
• the anaerobic adhesive is cured by crimping the adhesive composition between the adherends to block air.
• the squeezed part comes into contact with air, so that the curing reaction is hindered and the curing is poor. There is a problem that causes. Further, even when the clearance between the adherends is large, there is a problem that the pressure cannot be sufficiently crimped and the air cannot be completely blocked, causing poor curing.
• Instant adhesive usually contains cyanoacrylate as the main component and cures in a very fast time, so it has excellent workability. However, since the obtained cured product is brittle and has low adhesiveness, it is not suitable for structural applications where durability is required.
• SGA consists of a first agent containing an organic peroxide and a second agent containing a reducing agent that decomposes the organic peroxide contained in the first agent to generate radicals.
• the SGA is generally a two-component main agent type in which both the first agent and the second agent contain a main component such as a polymerizable (meth) acrylic monomer or an elastomer.
• the characteristic of the two-component main agent type SGA is that it does not require accurate measurement of the two agents, and even if the measurement and mixing are incomplete, it can be cured in a few minutes to several tens of minutes at room temperature by just contacting the two agents. It is widely used from the fields of electrical and electronic parts to the fields of civil engineering and construction because it has excellent properties, high tensile elongation, and good hardening of the exposed part. Regarding such SGA, various proposals have been made as described in Patent Documents 1 to 5.
• Patent Document 1 reports that the use of a flexible (meth) acrylate or urethane prepolymer exhibits high flexibility and can alleviate the strain generated in a metal adherend due to curing shrinkage stress.
• the adhesion regarding the resin adherend there is no description about heat cycle resistance or heat resistance.
• Patent Document 2 reports a technique for improving the low temperature characteristics of SGA by using a liquid elastomer. However, Patent Document 2 does not mention that both flexibility and adhesion are compatible. Patent Document 2 does not mention heat cycle resistance and heat resistance, and does not describe tensile elongation.
• Patent Document 3 reports that a composition having high stress relaxation property can be provided by reacting a (meth) acrylate having a hydroxyl group with a polyisocyanate having an isocyanate group.
• a composition having high stress relaxation property can be provided by reacting a (meth) acrylate having a hydroxyl group with a polyisocyanate having an isocyanate group.
• the urethane bond formed by the reaction of the hydroxyl group and the isocyanate group is hydrolyzed, which is difficult in terms of durability.
• polyisocyanate having an isocyanate group is decomposed by reacting with water, and there is a problem in storage stability.
• Patent Document 4 reports a technique for improving the heat resistance of SGA by using zeolite. However, Patent Document 4 does not mention that both flexibility and adhesion are compatible.
• Patent Document 5 describes that a specific (meth) acrylate is used as a technique for improving the adhesion to the resin.
• polycarbonate resin, ABS (acrylonitrile-butadiene-styrene) resin, phenol resin, epoxy resin, etc. which are resin materials often used as structural members, have an aromatic skeleton as a constituent unit thereof, and similarly have an aromatic skeleton.
• phenoxyethyl (meth) acrylate which has a group skeleton, improves adhesion to the adherend.
• (meth) acrylates having an aromatic skeleton generally do not have high flexibility of the obtained cured product due to its rigid structure. In other words, the problem of trade-off between resin adhesion and flexibility could not be solved.
• the present invention can provide the following.
• composition according to aspect 1 wherein the component comprises a bisphenol structural portion.
• Aspect 3 The composition according to aspect 1 or 2, wherein the number of aromatic rings contained in the component is 4 or more per molecule.
• Aspect 4 The composition according to any one of aspects 1 to 3, wherein the number of hydroxyl groups contained in the component is 5 or less per molecule.
• Aspect 5 The composition according to any one of aspects 1 to 4, wherein the content of the component (1) is 0.1 part by mass or more and 20 part by mass or less based on a total of 100 parts by mass of the component (1) and the component (2). thing.
• Aspect 6 The composition according to any one of aspects 1 to 5, wherein the component has a (meth) acryloyl group.
• Aspect 7 The composition according to any one of aspects 1 to 6, wherein the component (1) is a reaction product of a lactone-modified (meth) acrylate monomer, an acid anhydride, and an epoxy monomer.
• Aspect 8 The composition according to any one of aspects 1 to 7, wherein the component has a (meth) acryloyl group.
• Aspect 9 The composition according to any one of aspects 1 to 8, wherein the weight average molecular weight Mw of the component (1) measured by the GPC method is 1,000 or more.
• Aspect 10 (4) The composition according to any one of aspects 1 to 9, which contains an elastomer.
• Aspect 11 The composition according to any one of aspects 1 to 10, which contains a reducing agent.
• a two-dosage form wherein the first agent and the second agent when divided into the first agent and the second agent contain at least (3) a polymerization initiator, and the second agent does not contain at least (3) a polymerization initiator.
• the composition according to any one of 1 to 11.
• Aspect 13 Aspect 1 of the two-dosage form, wherein the first agent when divided into the first agent and the second agent contains at least (3) a polymerization initiator, and the second agent contains at least (5) a reducing agent.
• the composition according to any one of 1 to 11.
• a curable composition comprising the composition according to any one of aspects 1 to 13.
• Aspect 15 An adhesive composition containing the curable composition according to aspect 14.
• Aspect 17 An adhesion method comprising applying the adhesive composition according to aspect 15 to an adherend and adhering the adherend.
• a compound having any of the following structural formulas are independently hydrogen atoms or methyl groups, respectively.
• k, m, n, p, and q are each independently an integer greater than or equal to 0.
• R 1 and R 2 in the formula are independently hydrogen atoms or methyl groups, respectively.
• k, m, n, p, and q are each independently an integer greater than or equal to 0.
• Aspect 19 The compound according to embodiment 18, wherein k is an integer greater than or equal to 1.
• the composition provided by the embodiment of the present invention has the effect of exhibiting flexibility and adhesion.
• the composition provided by the embodiment of the present invention has the effect of exhibiting, for example, excellent flexibility, heat cycle resistance, and heat resistance, and also exhibits excellent adhesion to both metals and resins. Be done.
• the term "monofunctional (meth) acrylate” means a (meth) acrylate having a single (meth) acryloyl group. Further, the "polyfunctional (meth) acrylate” means a (meth) acrylate having two or more (meth) acryloyl groups.
• composition that can be provided by the embodiment of the present invention has (1) an aromatic ring and a hydroxyl group, and the cured product thereof is JIS K7161-1. : 2014
• JIS K 7161-2 2014 Reactive compounds with a tensile elongation of 50% or more measured in an atmosphere of 23 ° C, and (2) Reactive compounds other than (1) above, ( 3) A polymerization initiator is included.
• the component is a novel component for giving the composition high adhesion to resins and metals and high flexibility as a cured product, and has high reactivity capable of copolymerizing with other reactive compounds. Have. Therefore, the component (1) needs to have a large tensile elongation at room temperature in the single cured product. On the other hand, the component (1) also has a rigid structure having an aromatic ring, but in addition to a large tensile elongation due to the presence of hydroxyl groups, it also has excellent adhesion to both metals and resins. Is possible.
• the component may be a reactive monomer or oligomer, and the reactive group is preferably a group having a carbon-carbon double bond. From the viewpoint of obtaining high reactivity, for example, a (meth) acryloyl group. May have one or more per molecule.
• the component (1) may be a monofunctional (meth) acrylate, a polyfunctional (meth) acrylate, or a mixture thereof.
• the component (1) preferably contains a bisphenol structural portion from the viewpoint of improving heat resistance. From the viewpoint of further improving the heat resistance, the number of aromatic rings contained in the component (1) is more preferably 4 or more per molecule.
• the number of hydroxyl groups contained in the component is preferably 5 or less per molecule from the viewpoint of improving the adhesiveness without affecting the heat resistance.
• the amount of the component (1) used is preferably 0.1 part by mass or more and 20 parts by mass or less, preferably 0.1 part by mass or more and 20 parts by mass when the total of the (1) component and the (2) component is 100 parts by mass. It is more preferably less than, and most preferably 1 part by mass or more and 15 parts by mass or less.
• the component is 0.1 parts by mass or more, high adhesion to the resin and metal and high flexibility as a cured product are improved. Further, when the component (1) is 20 parts by mass or less, the compatibility is improved and a uniform resin composition can be easily obtained.
• the weight average molecular weight Mw of the component is measured by a GPC (gel permeation chromatography) method, and is preferably 1,000 or more, more preferably 2,000 or more.
• the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less.
• the component (1) include a reaction product of a lactone-modified (meth) acrylate monomer, an acid anhydride, and an epoxy monomer.
• a lactone-modified (meth) acrylate monomer any lactone such as ⁇ -acetolactone, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone can be used.
• a product of the Praxel series manufactured by Daicel Co., Ltd. can be mentioned. can.
• BASF's Petrochemicals Specialty Monomers series products can also be mentioned.
• the trade name "HECLA” Hydroxyethylcaprolactone Acrylate can be used.
• the lactone-modified (meth) acrylate monomer can be synthesized and used from hydroxy (meth) acrylate and hydroxycarboxylic acid in addition to commercially available products. Lactone-modified (meth) acrylate by dehydration condensation of 2-hydroxyethyl (meth) acrylate (for example, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 6-hydroxycaproic acid (for example, manufactured by Chemwill Asia Co., LTD, etc.) Monomers can be obtained.
• carboxylic acid anhydride is preferable, and phthalic anhydride, benzoic anhydride, acetic anhydride, propionic anhydride, succinic anhydride, succinic anhydride, maleic anhydride, and 2,3-naphthalenedicarboxylic acid anhydride are preferable. Anything such as an object can be used. From the viewpoint of ease of reaction, cyclic carboxylic acid anhydride is preferable.
• epoxy monomer any one known as a raw material for an epoxy resin can be used, and one having an aromatic ring is preferable.
• epoxy monomers having an aromatic ring include compounds having a glycidyloxyphenyl group.
• examples of the compound having such a glycidyloxyphenyl group include bisphenol A type diglycidyl ether having the following structural formula.
• N in the equation is an integer greater than or equal to 0, preferably an integer from 0 to 3.
• R 1 and R 2 in the formula are independently hydrogen atoms or methyl groups, respectively.
• k, m, n, p, and q are each independently an integer of 0 or more, preferably an integer of 1 or more.
• k is 1 or more
• m + n is 2 to 25
• p and q may be 1 to 10
• more preferably k is 1 to 3
• m + n is 10 to 25
• p and q are 2. It may be up to 10.
• the asterisk in the formula indicates the place where the structural formula is originally connected, and is for the convenience of the description space.
• R 1 and R 2 in the formula are independently hydrogen atoms or methyl groups, respectively.
• k, m, n, p, and q are each independently an integer of 0 or more, preferably an integer of 1 or more.
• k is 1 or more
• m + n is 2 to 25
• p and q may be 1 to 10
• more preferably k is 1 to 3
• m + n is 10 to 25
• p and q are 2. It may be up to 10.
• the asterisk in the formula indicates the place where the structural formula is originally connected as described above.
• (1) the elongation of the cured product of the component alone shall be measured as follows. (1) Add 3.0 parts by mass of the photoinitiator to 100 parts by mass of the component and stir. Pour the stirred mixture onto a PET film and apply with a bar coater to a thickness of 0.1 mm. This is irradiated with ultraviolet rays and cured to obtain a cured product. Using this cured product, perform a tensile test in accordance with JIS K7161-2: 2014 in an environment of 23 ° C, and measure the tensile elongation. The unit of tensile elongation is%, which indicates the increment from the length of the cured product before the test.
• the elongation of the cured product of the component alone is 50% or more, preferably 70% or more, and more preferably 100% or more.
• the elongation of the cured product of the component alone is preferably 500% or less, more preferably 300% or less, and most preferably 200% or less.
• the reactive compound which is the component (2) is defined as excluding the component (1) and has a function of dissolving other components of the composition.
• the component (2) is preferably one or more monomers selected from (meth) acrylate and hydroxyalkyl (meth) acrylate having a hydrocarbon group.
• a hydrocarbon group is preferably an unsubstituted or substituted hydrocarbon group having 1 to 32 carbon atoms.
• the hydrocarbon group may be a linear, branched or alicyclic aliphatic group, aromatic group, or a combination thereof. From the viewpoint of obtaining sufficient solubility of other components, it is preferable that the component (2) contains at least one (meth) acrylate or hydroxyalkyl (meth) acrylate having an aliphatic group.
• the component (2) may be a monofunctional (meth) acrylate, a polyfunctional (meth) acrylate, or a mixture thereof.
• Examples of the component (2) having a linear or branched aliphatic group and being monofunctional include methyl (meth) acrylate, ethyl (meth) acrylate, hexyl (meth) acrylate, and octyl (meth).
• Hydroxyalkyl (meth) acrylates such as acrylates can be mentioned.
• monofunctional (meth) acrylates include 2-hydroxyethyl (meth) acryloyl phosphate, 4-butylhydroxy (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, and glycerin mono.
• Examples of the alicyclic or aromatic monofunctional (meth) acrylate include adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and cyclohexyl (meth).
• polyfunctional (meth) acrylate examples include di (meth) acrylate, tri (meth) acrylate, and tetra (meth) acrylate having a linear, branched, or alicyclic aliphatic group or aromatic group. Be done.
• Specific examples of such polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and ethoxylated bisphenol A di.
• the component (2) is one of the group consisting of (2-1) alkyl (meth) acrylate, (2-2) hydroxyalkyl (meth) acrylate, and (2-3) (meth) acrylate having a cyclic structure. More than a species is preferable, and it is more preferable to contain a combination of (2-1) alkyl (meth) acrylate, (2-2) hydroxyalkyl (meth) acrylate, and (2-3) (meth) acrylate having a cyclic structure. preferable.
• a (meth) acrylate having an aliphatic group is preferable.
• the (meth) acrylate represented by the following general formula (A) is preferable.
• General formula (A) ZOR 1 In the formula, Z represents a (meth) acryloyl group, and R 1 represents an alkyl group having 1 to 20 carbon atoms.
• R 1 in the above formula is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.
• the number of carbon atoms is 20 or less, the surface curability is improved, stickiness is suppressed, and the curing speed can be improved.
• alkyl (meth) acrylates examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
• methyl (meth) acrylate is preferable because it has a large effect.
• the (meth) acrylate represented by the general formula (B) is preferable.
• General formula (B) ZO- (R 2 O) s-H wherein, Z is shown a (meth) acryloyl group, R 2 is -C 2 H 4 -, - C 3 H 6 -, - CH 2 CH (CH 3) -, - C 4 H 8 - or -C 6 H 12 ⁇ , and s is an integer from 1 to 10.
• hydroxyalkyl (meth) acrylates examples include 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, hydroxybutyl (meth) acrylates, and the like, and one or more of these may be used. Can be used. Among these, 2-hydroxyethyl (meth) acrylate and / or 2-hydroxypropyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is more preferable, because the effect is large.
• a combination of (2-1) alkyl (meth) acrylate, (2-2) hydroxyalkyl (meth) acrylate, and (2-3) (meth) acrylate having a cyclic structure is contained as a component, the combination thereof.
• the content ratio is a mass ratio of (2-1) alkyl (meth) acrylate, (2-2) hydroxyalkyl (meth) acrylate, and (2-3) (meth) acrylate having a cyclic structure in a total of 100 parts by mass.
• (2-1) :( 2-2): (2-3) 10 to 90: 2 to 50: 3 to 20, more preferably 30 to 70:10 to 50: 3 to 20, 40 to 40. Most preferably 60:20 to 40: 5 to 20.
• the amount of the component (2) used is preferably 80 parts by mass or more and 99.9 parts by mass or less, and more than 80 parts by mass and 99.9 parts by mass, when the total of the (1) component and the (2) component is 100 parts by mass. It is more preferably 85 parts by mass or more and 99 parts by mass or less.
• the polymerization initiator has a function of advancing the polymerization reaction.
• an organic peroxide is preferable.
• the organic peroxide include cumene hydroperoxide, paramentan hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, tertiary butyl peroxide and the like. .. One or more of these can be used. Of these, cumene hydroperoxide is preferred in terms of reactivity and storage stability.
• the amount of the polymerization initiator added is preferably 0.5 to 10 parts by mass, preferably 1 to 7 parts by mass, based on 100 parts by mass of the total of the components (1), (2) and (4) used as needed. Is more preferable. If it is 0.5 parts by mass or more, the curing rate is appropriate, and if it is 10 parts by mass or less, the storage stability is appropriate.
• the resulting composition has a sufficiently reduced internal stress after curing due to the synergistic effect of containing the components.
• the composition also has excellent adhesion to adherends such as resin and metal, it is considered that the composition can sufficiently resist the internal stress and adhere to the adherend, resulting in extremely excellent heat cycle resistance. Further, according to the composition, adhesion between different materials is possible.
• the composition may be of a two-dosage form, preferably containing at least component (3) in the first agent and not containing component (3) in the second agent.
• the second agent contains a reducing agent that decomposes the component (3) and generates radicals.
• Elastomer is added for the purpose of improving the toughness of the composition or for the purpose of improving the viscosity.
• the "elastomer” refers to a polymer substance having rubber-like elasticity at room temperature, and those capable of being dissolved or dispersed in the components (1) and (2) are preferable.
• thermoplastic elastomers such as adipate type and PTMG type
• polyester-based thermoplastic elastomers such as polybutylene terephthalate-polytetramethylene glycol multi-block polymer
• polyamide-based heat such as nylon-polyol block copolymers and nylon-polyester block copolymers.
• plastic elastomers 1,2-polybutadiene-based thermoplastic elastomers, and vinyl chloride-based thermoplastic elastomers. As long as these elastomer components have good compatibility, one kind or two or more kinds can be used.
• polybutadiene or modified polybutadiene can be used.
• methyl (meth) acrylate-butadiene-styrene copolymer and / or (meth) acrylonitrile-butadiene rubber is preferable, and (meth) acrylonitrile-butadiene rubber is more preferable in terms of solubility and adhesion to the compound. preferable.
• the amount of the elastomer component added is preferably 5 to 35 parts by mass, more preferably 10 to 30 parts by mass, based on 100 parts by mass of the total of the components (1) and (2). (4) When the component is 5 parts by mass or more, the viscosity and adhesiveness are improved, and when the component is 35 parts by mass or less, the viscosity is appropriate and the workability is improved.
• the reducing agent that generates radicals may be any known reducing agent that decomposes the component (3) and generates radicals.
• the reducing agent include metal salts of organic acids, ⁇ -diketone chelate, aromatic amines and / or pyridine derivatives, tertiary alkyl amines, thiourea derivatives and the like. Of these, thiourea derivatives are preferred.
• the thiourea derivative include 1-acetyl-2-thiourea, benzoylthiourea, N, N-diphenylthiourea, N, N-diethylthiourea, N, N-dibutylthiourea, tetramethylthiourea and the like. Of these, 1-acetyl-2-thiourea is preferred.
• the amount of the reducing agent added is preferably 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, based on 100 parts by mass of the total of the components (1), (2) and (4) used as needed. More preferred. If it is 0.1 part by mass or more, the curing rate is appropriate, and if it is 10 parts by mass or less, the storage stability is appropriate.
• a curable composition containing the above composition can be provided.
• an adhesive composition comprising the curable composition described above can be provided.
• the adhesive composition can provide a bonded body obtained by adhering an adherend (for example, a metal or a resin), and a method for adhering the adherend.
• the composition in a preferred embodiment has a tensile strain (tensile elongation) of 20% or more (that is, excellent low temperature flexibility) in a tensile test conducted in an atmosphere of ⁇ 20 ° C. in accordance with JIS K7161-1: 2014. ) Is preferable, and more than 20% is more preferable.
• the composition in a preferred embodiment preferably has a tensile shear adhesive strength of 1 MPa or more after 24 hours with respect to the resins measured by the method specified in JIS K 6850: 1999, or the fracture state is cohesive fracture. Is preferable. More preferably, the tensile shear adhesive strength may be 1 MPa or more and the fracture state may be cohesive fracture. The tensile shear adhesive strength may be more than 1 MPa.
• the composition in a preferred embodiment preferably has a tensile shear adhesive strength of 10 MPa or more after 24 hours with respect to the metals measured by the method specified in JIS K 6850: 1999, or the fracture state is cohesive fracture. Is preferable. More preferably, the tensile shear adhesive strength may be 10 MPa or more and the fracture state may be cohesive fracture. The tensile shear adhesive strength may be more than 10 MPa.
• Aggregate fracture is preferable in the fractured state. This is because cohesive fracture has adhesiveness at the interface between the composition and the adherend. In the interfacial fracture, the adhesiveness at the interface between the composition and the adherend is smaller than that in the cohesive fracture.
• the composition in a preferred embodiment has a storage modulus at 120 ° C. measured using a dynamic viscoelasticity measuring device in a heating rate of 2 ° C./min, a temperature range of -50 to 150 ° C., a frequency of 1 Hz, and a tensile mode.
• a storage modulus at 120 ° C. measured using a dynamic viscoelasticity measuring device in a heating rate of 2 ° C./min, a temperature range of -50 to 150 ° C., a frequency of 1 Hz, and a tensile mode.
• it is preferably 2.0 MPa or more (that is, excellent heat cycle resistance and heat resistance), and more preferably more than 2.0 MPa.
• phthalic anhydride (reagent grade manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 148 g / mol) 29.6 g
• 2,2-bis (4-glycidyloxyphenyl) propane (EXA-850CRP manufactured by DIC Co., Ltd., molecular weight: 340 g) / mol) 34 g
• triphenylphosphine Hokuko TPP manufactured by Hokuko Chemical Industry Co., Ltd., molecular weight: 262 g / mol
• the obtained colorless viscous liquid product A is dissolved in deuterated chloroform (reagent grade manufactured by Tokyo Chemical Industry Co., Ltd.) to prepare a 3% by mass solution, and then 1 H-nuclear magnetic resonance measurement ( 1 H-). NMR) was performed.
• the 1 H-NMR analysis data of the obtained colorless viscous liquid product A was as follows.
• the compounds obtained as described above were used as the component (1) and blended with the materials shown in the table below to prepare the respective compositions.
• the amounts in the table are shown in parts by mass.
• Methyl methacrylate Acryester M (manufactured by Mitsubishi Chemical Holdings) 2-Hydroxyethyl methacrylate: HEMA (manufactured by Nippon Shokubai Co., Ltd.)
• HEMA manufactured by Nippon Shokubai Co., Ltd.
• Isobornyl acrylate Light acrylate IB-XA (manufactured by Kyoeisha Chemical Co., Ltd.)
• ATU manufactured by Sanuki Chemical Industry Co., Ltd.
• Resin adhesion A test piece (manufactured by Test Piece) with dimensions of 2.0 x 25 x 100 mm using Teijin's polycarbonate resin "Panlite L1225" as a test piece was used as it was without pretreatment.
• the tensile shear adhesive strength test was performed and measured using a universal testing machine Instron model 4467 (manufactured by Instron) in accordance with JIS K 6850: 1999 under standard conditions (23 ° C). The shear strength when the test pieces were overlapped and adhered was determined in MPa units.
• a galvanized chromate steel sheet (manufactured by Testpiece) with dimensions of 1.6 x 25 x 100 mm was purchased as a test piece and used as it was without pretreatment.
• the tensile shear adhesive strength test was performed and measured using a universal testing machine Instron model 4467 (manufactured by Instron) in accordance with JIS K 6850: 1999 under standard conditions (23 ° C). The shear strength when the test pieces were overlapped and adhered was determined in MPa units.
• Heat cycle resistance / heat resistance A strip-shaped cured product having dimensions of 0.5 ⁇ 5 ⁇ 40 mm was used as a test piece.
• DMS7100 dynamic viscoelasticity measuring device
• a reactive compound having an aromatic ring and a hydroxyl group and having a tensile elongation of 50% or more measured in an atmosphere of 23 ° C. according to JIS K7161-2: 2014 of the cured product is used as the component (1). All of Examples 1 to 3 showed excellent results in all the evaluation items.
• Comparative Example 1 in which the component (1) was not used, the low temperature flexibility and the resin adhesion were inferior.
• Comparative Example 8 in which only the component (1) was used was also inferior in resin adhesion and metal adhesion.
• Comparative Examples 2 to 7 using various control components the performance of any of them was inferior.
• composition provided by the embodiment of the present invention has the effect of exhibiting excellent flexibility, heat cycle resistance and heat resistance, and also exhibiting excellent adhesion to both metals and resins.
• Patent Document 4 reports a technique for improving the heat resistance of SGA by using zeolite.
• zeolite which is an inorganic compound
• the flexibility is generally reduced.
• the problem of trade-off between heat cycle resistance / heat resistance and flexibility could not be solved.
• the heat-sensitive alkylene chain portion must be lengthened in order to improve the flexibility, and then the heat resistance is increased. The problem of sacrificing cycleability and heat resistance could not be solved.
• the embodiment of the present invention can solve the above-mentioned problems.

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• Polymers & Plastics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Macromonomer-Based Addition Polymer (AREA)
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• 2021
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