CN116715939A - Curable resin composition, adhesive, and adhesive method - Google Patents

Curable resin composition, adhesive, and adhesive method Download PDF

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Publication number
CN116715939A
CN116715939A CN202310191182.4A CN202310191182A CN116715939A CN 116715939 A CN116715939 A CN 116715939A CN 202310191182 A CN202310191182 A CN 202310191182A CN 116715939 A CN116715939 A CN 116715939A
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China
Prior art keywords
curable resin
resin composition
viscosity
composition according
acid
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CN202310191182.4A
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Chinese (zh)
Inventor
川口纯奈
富永大雅
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Abstract

Disclosed is a curable resin composition which has excellent fracture linearity, adhesion, and shape stability. In one embodiment, the curable resin composition comprises (A) a curable resin, (B) a BET specific surface area of 5m 2 Above/gCalcium carbonate, and (C) a curing agent.

Description

Curable resin composition, adhesive, and adhesive method
Technical Field
The present invention relates to a curable resin composition, an adhesive, and an adhesive method.
Background
Curable resin compositions have been used for a variety of purposes. For example, in the manufacture of electronic devices such as camera modules (camera modules), curable resin compositions are sometimes used to bond a plurality of members to each other. Such a curable resin composition is usually used by coating.
In the case of coating a resin composition, stable and good coating is required. In this regard, patent document 1 (japanese patent application laid-open No. 2002-177843) discloses a dispenser device having a specific structure as a dispenser device capable of stably performing good coating even when a paste having high viscosity and high thixotropic property is applied.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2002-177843.
Disclosure of Invention
Problems to be solved by the invention
In order to impart properties such as toughness, high heat resistance, and high reliability to a curable resin composition used as an adhesive or the like, it is sometimes necessary to use a curable resin having a high viscosity or a curable resin in a solid state.
However, when a curable resin having a high viscosity or a curable resin in a solid state is blended, the resin composition has tackiness. As a result, the coatability may be deteriorated. For example, in the case where the resin composition is discharged through a nozzle at the time of coating, stringing will easily occur. That is, the broken linearity becomes poor. As a result, the takt time (takt time) is liable to become long. In addition, the resin composition also becomes easy to adhere to the outside of the target site.
In order to improve the fracture linearity, the addition of an inorganic filler is also considered. However, in this case, the adhesion to the object to be bonded is likely to be lowered. In addition, thixotropic properties may be reduced. That is, the shape stability (shape retention) of the resin composition after coating is lowered, and the coated portion is easily spread after coating.
Therefore, it is difficult to improve the breaking line, the adhesion and the shape stability in a balanced manner.
Accordingly, an object of the present invention is to provide a curable resin composition having improved fracture linearity, adhesion and shape stability in a balanced manner (good balance).
Means for solving the problems
The present inventors have studied and found that the above problems can be solved by the following means.
[1]A curable resin composition comprising (A) a curable resin, (B) a BET specific surface area of 5m 2 Calcium carbonate of a ratio of/g or more, and (C) a curing agent.
[2] The curable resin composition according to [1], wherein the (A) curable resin comprises: at least one resin selected from a high-viscosity curable resin having a viscosity of 100 Pa.s or more as measured at 25 ℃ and 1rpm by an E-type viscometer and a solid curable resin which is a resin solid at 25 ℃.
[3] The curable resin composition according to [2], wherein the high-viscosity curable resin and the solid curable resin are 5 to 100 parts by mass per 100 parts by mass of the curable resin (A).
[4] The curable resin composition according to any one of [1] to [3], wherein the viscosity measured with an E-type viscometer at 25℃and 1rpm is 10 to 500 Pa.s.
[5] The curable resin composition according to any one of [1] to [4], wherein,
when the viscosity measured with an E-type viscometer at 25 ℃ and 1rpm is designated as V1 and the viscosity measured with an E-type viscometer at 25 ℃ and 10rpm is designated as V2, the ratio (V1/V2) of the viscosity V1 to the viscosity V2 of the curable resin composition is 1.5 to 6.0; or alternatively
When the viscosity measured with an E-type viscometer at 25℃and 2rpm is designated as V3 and the viscosity measured with an E-type viscometer at 25℃and 20rpm is designated as V4, the ratio (V3/V4) of the viscosity V3 to the viscosity V4 of the curable resin composition is 1.5 to 6.0.
[6] The curable resin composition according to any one of [1] to [5], wherein the (A) curable resin comprises at least one selected from the group consisting of an epoxy resin and a compound having a (meth) acryloyl group.
[7] The curable resin composition according to any one of [1] to [6], wherein the component (A) comprises an epoxy resin.
[8]According to [1]]～[7]The curable resin composition according to any one of (B) a BET specific surface area of calcium carbonateProduct is 5m 2 Above/g and 50m 2 And/g or less.
[9] The curable resin composition according to any one of [1] to [8], wherein the (C) curing agent comprises a polythiol compound having 2 or more mercapto groups in 1 molecule.
[10] The curable resin composition according to any one of [1] to [9], wherein the (A) curable resin is 5 to 80 parts by mass per 100 parts by mass of the nonvolatile component of the curable resin composition.
[11] The curable resin composition according to any one of [1] to [10], wherein the (B) calcium carbonate is 3 to 80 parts by mass relative to 100 parts by mass of a nonvolatile component of the curable resin composition.
[12] The curable resin composition according to [1] to [11], wherein the (C) curing agent is 5 to 80 parts by mass per 100 parts by mass of the nonvolatile component of the curable resin composition.
[13] The curable resin composition according to any one of [1] to [12], which is applied by being discharged from a nozzle.
[14] An adhesive comprising the curable resin composition of any one of [1] to [13 ].
[15] The adhesive according to [14], which is used for adhesion between constituent members of a camera module.
[16] A bonding method comprising the step of discharging the curable resin composition of any one of [1] to [13] from a nozzle.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a curable resin composition having improved fracture linearity, adhesion, and shape stability in a balanced manner.
Detailed Description
The curable resin composition according to the present embodiment comprises (A) a curable resin and (B) a BET specific surface area of 5m 2 Calcium carbonate of a ratio of/g or more, and (C) a curing agent. According to the present embodiment, a BET specific surface area of 5m is blended 2 Calcium carbonate of not less than/g, thus being capable of improving the breaking line, the adhesion and the shape stability in a balanced manner.
The components are described in detail below.
(A) Curable resin
The curable resin is not particularly limited as long as it has a function of curing by heat, ultraviolet rays, or the like.
The content of the curable resin (a) in the curable resin composition is, for example, 5 to 80 parts by mass, preferably 20 to 80 parts by mass, and more preferably 30 to 70 parts by mass, relative to 100 parts by mass of the nonvolatile component of the curable resin composition.
Examples of the curable resin include at least one selected from epoxy resins, compounds having a (meth) acryloyl group, silicone resins, phenolic resins, melamine resins, and unsaturated polyester resins. The curable resin preferably contains an epoxy resin or a compound having a (meth) acryloyl group, and particularly preferably contains an epoxy resin.
Examples of the epoxy resin include polyglycidyl ethers obtained by reacting a polyhydric phenol such as bisphenol a, bisphenol F, bisphenol AD, catechol, resorcinol, or a polyhydric alcohol such as glycerin or polyethylene glycol with epichlorohydrin; glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β -hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin; an epoxidized phenol novolac resin (Epoxidized Phenolic Novolac Resin), an epoxidized cresol novolac resin (Epoxidized Cresol Novolac Resin), an epoxidized polyolefin, a cycloaliphatic epoxy resin, other urethane-modified epoxy resins, and the like.
The "(meth) acryl" means one or both of acryl and methacryl.
Examples of the compound having a (meth) acryloyl group include: beta-carboxyethyl (meth) acrylate, isobornyl (meth) acrylate, octyl/decyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified ortho-phenylphenol (meth) acrylate, EO-modified para-cumylphenol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, omega-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) phthalate 2-hydroxy-3-phenoxypropyl (meth) acrylate, dipropylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, PO modified neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, EO modified isocyanuric acid di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, polyurethane having (meth) acryloyl groups, polyesters having a (meth) acryloyl group, trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO-modified isocyanuric acid (tri) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, glycerol propoxytri (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol (penta/hexa) (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified diglycerol tetra (meth) acrylate, epoxyacrylate, and the like. The epoxy acrylate may also be referred to as an epoxy resin.
Preferably, the curable resin contains at least one resin selected from the group consisting of a high-viscosity curable resin and a solid curable resin.
The "high-viscosity curable resin" is a resin having a viscosity of 100 pas or more as measured by an E-type viscometer at 25℃and 1 rpm. The viscosity (E-type viscometer, 25 ℃ C., 1 rpm) of the high-viscosity curable resin is preferably 100 to 2000 Pa.s, more preferably 120 to 1500 Pa.s.
The "high-viscosity curable resin" is preferably an epoxy resin. When the high-viscosity curable resin is an epoxy resin, the epoxy equivalent is, for example, 50 to 700g/eq, preferably 50 to 500g/eq, more preferably 100 to 450g/eq, and still more preferably 150 to 450g/eq.
The epoxy equivalent is the mass of the epoxy resin corresponding to 1 epoxy group, and can be measured in accordance with JIS K7236 (2009).
Specific examples of such a high-viscosity curable resin include "EXA-4816" (manufactured by DIC Co., ltd.), "MX-135" (manufactured by Kaneka Co., ltd.), and "EA-1010N" (manufactured by Xinzhongcun chemical industry Co., ltd.).
The "solid curable resin" is a curable resin that is solid at 25 ℃.
In a preferred embodiment, the curable resin includes a solid curable resin as an epoxy resin. When the solid curable resin is an epoxy resin, the epoxy equivalent is, for example, 800 to 1200g/eq, preferably 850 to 1100g/eq, and more preferably 900 to 1000g/eq.
Specific examples of such solid curable resins include "1004AF" (manufactured by mitsubishi chemical corporation).
By including the high-viscosity curable resin or the solid curable resin, the toughness, the high heat resistance, the high reliability, and the like can be improved. On the other hand, when such a resin is contained, the viscosity of the resin composition increases, and the broken linearity generally deteriorates. However, according to the present embodiment, the problem of linearity can be solved by using calcium carbonate. Therefore, even when a high-viscosity curable resin or a solid curable resin is contained, a curable resin excellent in the breaking line can be realized.
The content (total amount) of the high-viscosity curable resin and the solid curable resin is, for example, 5 to 100 parts by mass relative to 100 parts by mass of the curable resin.
In addition, the curable resin may contain a low-viscosity curable resin in addition to the high-viscosity curable resin and/or the solid curable resin.
The "low-viscosity curable resin" is a resin having a viscosity of less than 100 Pa.s (type E viscometer, 25 ℃ C., 1 rpm). The viscosity (25 ℃ C., 1 rpm) of the "low-viscosity curable resin" is preferably 1 to 50 Pa.s, more preferably 5 to 30 Pa.s.
By using a low-viscosity curable resin, the viscosity of the curable resin composition can be adjusted to a desired viscosity.
The content of the low-viscosity curable resin is, for example, 5 to 90 parts by mass, preferably 50 to 85 parts by mass, relative to 100 parts by mass of the curable resin.
In a preferred embodiment, the low viscosity curable resin is an epoxy resin. In this case, the epoxy equivalent is, for example, 150 to 300g/eq, preferably 170 to 250g/eq.
Specific examples of such a low-viscosity curable resin include "YL-980" (manufactured by Mitsubishi chemical corporation) and the like.
(B) Calcium carbonate
As calcium carbonate, as described above, a BET specific surface area of 5m can be used 2 And/g or more of calcium carbonate. The BET specific surface area can be measured in accordance with JIS Z8830 "specific surface area measurement method based on gas-adsorbed powder (solid)". The BET specific surface area can be measured by an automatic specific surface area measuring device, and examples of the automatic specific surface area measuring device include "Macsorb HM-1210" manufactured by Mountech, inc.
By using a BET specific surface area of 5m 2 Calcium carbonate of not less than/g can improve the fracture linearity, shape stability and adhesion in a balanced manner.
The BET specific surface area is less than 5m 2 In the case of the ratio/g, it is difficult to obtain desired shape stability, and the adhesion is also lowered.
In addition, when other inorganic fillers such as silica are used instead of calcium carbonate, the fracture linearity, shape stability and adhesion cannot be improved uniformly.
The BET specific surface area of the calcium carbonate was 5m 2 The ratio of the total weight of the catalyst to the total weight of the catalyst is not less than/g, preferably 6m 2 Preferably at least/g, more preferably 7m 2 Preferably at least/g, more preferably 8m 2 And/g. In addition, the BET specific surface area is preferably 50m 2 Preferably less than or equal to/g, more preferably 40m 2 Preferably less than or equal to/g, more preferably 35m 2 Preferably less than or equal to/g, particularly preferably 30m 2 And/g or less.
The content of calcium carbonate is, for example, 3 to 80 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass, based on 100 parts by mass of the nonvolatile component of the curable resin composition.
(C) Curing agent
The curing agent is a substance having a function of curing the curable resin by heat and/or ultraviolet irradiation or the like. The curing agent is not particularly limited as long as it has a function of curing the curable resin.
Preferably, as the curing agent, a thiol compound having a mercapto group can be used. More preferably, the thiol compound is a polythiol compound having 2 or more mercapto groups in 1 molecule. That is, a polyfunctional thiol compound can be preferably used. When the polyfunctional thiol compound is used, the curable resin composition can be rapidly cured at a low temperature. In addition, since the viscosity of the polyfunctional thiol compound is low, even when a resin having a high viscosity is used, the viscosity of the entire resin composition is easily reduced.
The number of mercapto groups in the 1-molecule polythiol compound is preferably 2 to 6, more preferably 2 to 4, and still more preferably 2 to 3.
Specific examples of the polythiol compound include partial esters of a polyhydric alcohol and a mercapto organic acid, full esters of a polyhydric alcohol and a mercapto organic acid, and the like. The partial ester is an ester of a polyhydric alcohol and a carboxylic acid, and means an ester in which a part of hydroxyl groups of the polyhydric alcohol form an ester bond. The full ester is an ester in which all hydroxyl groups of the polyol form ester bonds.
Examples of the polyhydric alcohol include ethylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like.
Examples of the mercapto organic acid include: mercaptoaliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid (e.g., 3-mercaptopropionic acid), and mercaptobutyric acid (e.g., 3-mercaptobutyric acid, 4-mercaptobutyric acid); esters containing mercapto groups and carboxyl groups obtained by esterification of hydroxy acids with mercapto organic acids; mercapto aliphatic dicarboxylic acids such as mercapto succinic acid and dimercaptosuccinic acid (e.g., 2, 3-dimercaptosuccinic acid); mercapto aromatic monocarboxylic acids such as mercapto benzoic acid (e.g., 4-mercapto benzoic acid); etc. The mercapto aliphatic monocarboxylic acid has preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Among the mercapto organic acids, mercapto aliphatic monocarboxylic acids having 2 to 8 carbon atoms are preferable, and thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid and 4-mercaptobutyric acid are more preferable, and 3-mercaptopropionic acid is still more preferable.
Specific examples of the partial ester of a polyhydric alcohol and a mercapto organic acid include: trimethylolethane bis (mercaptoacetate), trimethylolethane bis (3-mercaptopropionate), trimethylolethane bis (3-mercaptobutyrate), trimethylolethane bis (4-mercaptobutyrate), trimethylolpropane bis (mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), trimethylolpropane bis (3-mercaptobutyrate), trimethylolpropane bis (4-mercaptobutyrate), pentaerythritol tris (mercaptoacetate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tris (3-mercaptobutyrate), pentaerythritol tris (4-mercaptobutyrate), dipentaerythritol tetrakis (mercaptoacetate), dipentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol tetrakis (4-mercaptobutyrate), and the like.
Specific examples of the full ester of the polyhydric alcohol and the mercapto organic acid include: ethylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (3-mercaptobutyrate), ethylene glycol bis (4-mercaptobutyrate), trimethylolethane tris (mercaptoacetate), trimethylolethane tris (3-mercaptopropionate), trimethylolethane tris (4-mercaptobutyrate), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (4-mercaptobutyrate), dipentaerythritol hexa (mercaptoacetate), dipentaerythritol hexa (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptobutyrate), dipentaerythritol hexa (4-mercaptobutyrate), and the like.
The content of the curing agent is, for example, 5 to 80 parts by mass, preferably 10 to 50 parts by mass, and more preferably 15 to 40 parts by mass, based on 100 parts by mass of the nonvolatile component of the curable resin composition.
(D) Other ingredients
The curable resin composition may contain other components in addition to the above components as needed. Examples of the other component include a storage stabilizer, a curing accelerator, a filler, a silane coupling agent, and a thermoplastic resin.
The storage stabilizer is used for extending the shelf life (pot life) of the curable resin composition. In particular, when a thiol compound is used as a curing agent, the shelf life of the curable resin composition is easily shortened. Therefore, it is preferable to add a storage stabilizer.
Examples of the storage stabilizer include boric acid ester compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides, and mercapto organic acids.
Examples of the borate compound include trimethyl borate, triethyl borate (TEB), tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tricodecyl borate, tricetyl borate, tricctadecyl borate, tris (2-ethylhexyl) oxy) borane, bis (1, 4,7, 10-tetraoxaundecyl) (1, 4,7,10, 13-pentaoxatetradecyl) (1, 4, 7-trioxaundecyl) borane, tribenzyl borate, triphenyl borate, tricresyl borate, triethanolamine borate, and the like.
Examples of the titanate compound include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraoctyl titanate.
Examples of the aluminate compound include triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, and trioctyl aluminate.
Examples of the zirconate compound include tetraethylzirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.
Examples of the isocyanate compound include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2, 6-dimethylphenyl isocyanate, toluene diisocyanate (e.g., 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate), 1, 5-naphthalene diisocyanate, diphenylmethane-4, 4' -diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, and bicycloheptane triisocyanate.
Examples of the carboxylic acid include saturated aliphatic monoacids such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, unsaturated aliphatic monoacids such as acrylic acid, methacrylic acid, crotonic acid, halogenated aliphatic acids such as monochloroacetic acid, dichloroacetic acid, monohydric hydroxyacetic acid, lactic acid, aliphatic aldehyde acid such as glyoxylic acid, racemic tartaric acid, keto acid, oxalic acid, malonic acid, succinic acid, and maleic acid, aromatic monoacids such as benzoic acid, halobenzoic acid, toluic acid, phenylacetic acid, cinnamic acid, mandelic acid, and aromatic polybasic acids such as phthalic acid and trimesic acid.
Examples of the acid anhydride include succinic anhydride, dodecenylsuccinic anhydride, maleic anhydride, adducts of methylcyclopentadiene and maleic anhydride, aliphatic or aliphatic polybasic acid anhydrides such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, and aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride.
Examples of the mercaptoorganic acid include mercaptoaliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid and dimercaptosuccinic acid, and mercaptoaromatic monocarboxylic acids such as mercaptoaliphatic monocarboxylic acids obtained by esterification of a hydroxy organic acid with a mercaptoorganic acid and mercaptobenzoic acid.
Among these, from the viewpoint of high versatility and safety and improved storage stability, the borate compound is preferable, triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate are more preferable, and triethyl borate is still more preferable.
The content of the storage stability improver is, for example, 0.001 to 50 parts by mass, preferably 0.05 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total content of the curable resin (a).
The curing accelerator is not particularly limited, and for example, a latent curing accelerator may be used. Examples of the latent curing accelerator include solid dispersion type latent curing accelerators. The solid dispersion type latent curing accelerator is a compound which is insoluble in the curable resin composition at room temperature (25 ℃) and becomes soluble by heating, and functions as a curing accelerator in the curable resin composition. Examples of the solid dispersion type latent curing accelerator include an imidazole compound which is solid at ordinary temperature and a solid dispersion type amine adduct type latent curing accelerator, but are not limited thereto. Examples of the solid dispersion type amine adduct-based latent curing accelerator include a reaction product of an amine compound and an epoxy compound (amine-epoxy adduct-based), a reaction product of an amine compound and an isocyanate compound or a urea compound (urea-based adduct-based), and the like. Among these, solid dispersion type amine adduct-based latent curing accelerators are preferred.
Examples of the imidazole compound that is solid at ordinary temperature include 2-heptadecylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2, 4-diamino-6- (2-methylimidazole- (1)) -ethyl s-triazine, 2, 4-diamino-6- (2 ' -methylimidazole- (1) ') -ethyl s-triazine-isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N- (2-methylimidazole-1-ethyl) -urea, N ' - (2-methylimidazole- (1) -ethyl) -adipoyl diamine, and the like, but are not limited thereto.
Examples of the epoxy compound that can be used as one of the raw materials for producing the solid dispersion type amine adduct-based latent curing accelerator (amine-epoxy adduct-based) include polyglycidyl ethers obtained by reacting a polyhydric phenol such as bisphenol a, bisphenol F, catechol, resorcinol, or a polyhydric alcohol such as glycerin or polyethylene glycol with epichlorohydrin; glycidyl ether esters obtained by reacting a hydroxy acid such as p-hydroxybenzoic acid or β -hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin; glycidyl amine compounds obtained by reacting epichlorohydrin with 4,4' -diaminodiphenylmethane, para-aminophenol, or the like; multifunctional epoxy compounds such as epoxy phenol novolac resins, epoxy cresol novolac resins, and epoxy polyolefin, monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate; and the like, but are not limited thereto.
The amine compound which can be used as a raw material for producing the solid dispersion type amine adduct-based latent curing accelerator may be an amine compound having 1 or more active hydrogens capable of undergoing an addition reaction with an epoxy group in the molecule and at least 1 or more functional groups selected from the group consisting of primary amino groups, secondary amino groups and tertiary amino groups in the molecule. Examples of such amine compounds include aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4' -diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4' -diaminodiphenylmethane and 2-methylaniline; heterocyclic compounds containing nitrogen atom such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2, 4-dimethylimidazoline, piperidine and piperazine; and the like, but are not limited thereto.
Among them, compounds having tertiary amino groups in the molecule are a raw material for forming a latent curing accelerator having excellent curing acceleration ability, and examples of such compounds include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-N-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, and primary or secondary amines having tertiary amino groups in the molecule such as imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2- (dimethylaminomethyl) phenol, 2,4, 6-tris (dimethylaminomethyl) phenol, N-. Beta. -hydroxyethylmorpholine, 2-dimethylaminoethylthiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N-dimethylcarbamic acid, N-dimethylglycine, N-nicotinic acid, N-dimethylhydrazine, alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule, such as N-dimethylpropionyl hydrazide, nicotinyl hydrazide, isonicotinyl hydrazide, and the like; etc.
In the case of producing a latent curing accelerator by subjecting the epoxy compound and the amine compound to an addition reaction, an active hydrogen compound having 2 or more active hydrogens in the molecule may be further added. Examples of such an active hydrogen compound include, but are not limited to, polyhydric phenols such as bisphenol a, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and novolac (phenolic novolac resin), polyhydric alcohols such as trimethylol propane, polycarboxylic acids such as adipic acid and phthalic acid, 1, 2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid.
As the isocyanate compound usable as a raw material for producing the solid dispersion type amine adduct-based latent curing accelerator, for example, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate and the like can be used; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate (e.g., 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate), 1, 5-naphthalene diisocyanate, diphenylmethane-4, 4' -diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, 1,3, 6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and compounds containing terminal isocyanate groups obtained by the reaction of these polyfunctional isocyanate compounds with an active hydrogen compound; etc. Examples of such a compound containing a terminal isocyanate group include an addition compound having a terminal isocyanate group obtained by a reaction of toluene diisocyanate and trimethylolpropane, an addition compound having a terminal isocyanate group obtained by a reaction of toluene diisocyanate and pentaerythritol, and the like, but are not limited thereto.
The urea compound that can be used as a raw material for producing the solid dispersion type amine adduct-based latent curing accelerator is exemplified by urea, thiourea, and the like, but is not limited thereto.
The solid dispersion type latent curing accelerator can be easily obtained, for example, by the following means: the above production raw materials are appropriately mixed, reacted at a temperature of room temperature to 200 ℃, cooled and solidified, and then pulverized, or reacted in a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, or the like, and after desolvation, the solid component is pulverized.
Typical examples of the solid dispersion type latent curing accelerator that is commercially available include, but are not limited to, amine-epoxy adduct systems (amine adduct systems) such as "PN-F" manufactured by Ajinomoto Fine-Techno Co., inc. "PN-23", "Ajicure PN-H", hardner X-3661S "manufactured by A.C. R., hardner X-3670S", and "NOVACURE HX-3742" manufactured by Asahi chemical Co., ltd., NOVACURE HX-3721", and urea-type adduct systems such as" FXE-1000 "and" FXR-1030 "manufactured by T & K TOKA.
The content of the curing accelerator is, for example, 0.1 to 100 parts by mass, preferably 1 to 60 parts by mass, more preferably 5 to 30 parts by mass, based on 100 parts by mass of the total content of the curable resin (a).
Examples of the filler include fine silica powder. When the micro-powder silica and the calcium carbonate are used together, the balance between thixotropic properties and adhesion may be easily achieved. In addition, when a solid dispersion type substance is used as a curing accelerator, the fine silica powder also functions as a precipitation inhibitor. Specific examples of such a fine silica powder include "RY-300" manufactured by AEROSIL Co., ltd.
The silane coupling agent can be used, for example, for improving adhesion and suppressing the falling-off of the inorganic filler.
The thermoplastic resin may be added for the purpose of viscosity adjustment or the like within a range that does not affect the effect of the present invention.
(E) Curable resin composition
The curable resin composition according to the present embodiment preferably has a viscosity of 10 to 500pa·s (E-type viscometer, 25 ℃, 1 rpm). The viscosity (E-type viscometer, 25 ℃ C., 1 rpm) of the curable resin composition is more preferably 30 to 450 Pa.s, still more preferably 30 to 400 Pa.s.
In addition, in the curable resin composition, when the viscosity measured with an E-type viscometer at 25℃and 1rpm is denoted as V1 and the viscosity measured with an E-type viscometer at 25℃and 10rpm is denoted as V2, the ratio of V1 to V2 (V1/V2) is preferably 1.5 to 6.0. The ratio (V1/V2) is more preferably 1.5 to 4.0, still more preferably 1.5 to 3.5.
Alternatively, in the curable resin composition, when the viscosity measured with an E-type viscometer at 25℃and 2rpm is denoted as V3 and the viscosity measured with an E-type viscometer at 25℃and 20rpm is denoted as V4, the ratio of the viscosity V3 to V4 (V3/V4) is preferably 1.5 to 6.0. The ratio (V3/V4) is more preferably 1.5 to 4.0, still more preferably 1.5 to 3.5.
The curable resin composition has good breaking properties. Specifically, the curable resin composition has a breakage of 15mm or less, preferably 10mm or less. The "broken line" can be measured by the method described in examples described below.
The curable resin composition has good adhesion. Specifically, the curable resin composition has, for example, 1.5N/mm 2 Above, preferably 2.0N/mm 2 The above, preferably 2.0 to 10.0N/mm 2 Is used for the bonding force of the rubber sheet. The "adhesion force" can be measured by the method described in examples described below.
The curable resin composition is preferably used as an adhesive. More preferably, the curable resin composition is used as an adhesive for bonding members constituting the electronic component to each other. Examples of the electronic component include a camera module. The curable resin composition is preferably an adhesive used by applying to LCP (liquid crystal polymer).
The curable resin composition is preferably of the one-component type. The one-component curable resin composition is a resin composition provided in a state where a curing agent and a curable resin are mixed in advance. When in use, the curable resin composition is applied to the necessary parts. The curable resin composition can be cured by heat, ultraviolet rays, or the like.
The curable resin composition is preferably discharged from a nozzle at the time of application. For example, in the dispenser, the syringe is filled, and the syringe is discharged to a necessary portion through the nozzle. When the curable resin composition is used by such a method, it is important to have good breaking line and shape stability. The curable resin composition according to the present embodiment can realize good breaking properties without deteriorating adhesion and shape stability. Therefore, the present invention is particularly suitable for use in applications where the liquid is discharged from a nozzle.
The method for producing the curable resin composition is not particularly limited, and can be carried out according to a known method. That is, the curable resin, calcium carbonate, and curing agent may be mixed with other components as needed.
The curable resin composition is also cured without particular difficulty, and this can be carried out according to a conventionally known method. For example, the applied curable resin composition may be cured by heating at a temperature of room temperature or higher. The heating temperature is, for example, 70 to 150℃and preferably 75 to 120 ℃. The heating time is, for example, 1 to 60 minutes, preferably 10 to 50 minutes, more preferably 15 to 45 minutes.
Examples
Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention should not be construed as being limited thereto.
[ preparation of curable resin composition ]
Curable resin compositions according to examples 1 to 9 and comparative examples 1 to 8 were prepared by mixing the components in the compounding compositions shown in tables 1 to 4. In the table, the amount of each component is referred to as a mass part.
Specifically, the amounts of curable resin and curing agent shown in the table were weighed into dedicated plastic containers. Then, the mixture was thoroughly mixed at about 2000rpm for about 30 seconds to 1 minute at room temperature of 25℃using a rotation and revolution MIXER "THINKY MIXER" (AWARING Takara) (ARE-310, manufactured by Nissan Co., ltd.) to obtain a liquid mixture. To this liquid mixture, calcium carbonate, silica, a storage stabilizer and a curing accelerator were added, and the mixture was mixed at 2000rpm for about 30 seconds to 1 minute at room temperature of 25 ℃ using a rotation/revolution mixer. Finally, the object curable resin composition was obtained by deaeration at 900rpm for 2 minutes under vacuum (pressure was set to 0) using an automatic revolution stirring deaerator HM-200W manufactured by Co-located fine machine Co.
The details of the materials used are as follows.
(1) Low viscosity curable resin
YL-980: bisphenol A type (BPA type) liquid epoxy resin, which is produced by Mitsubishi chemical corporation, has an epoxy equivalent of 190g/eq, a molecular weight of 380, and a viscosity of 10 to 20 Pa.s (E type viscometer, 25 ℃ C., 1 rpm).
(2) Solid curable resin
1004AF: bisphenol A type (BPA type) solid epoxy resin, which has an epoxy equivalent of 925g/eq, a molecular weight of 1850 and is solid at normal temperature, manufactured by Mitsubishi chemical corporation.
(3) High-viscosity curable resin
EXA-4816: modified epoxy resin produced by DIC Co., ltd., having an epoxy equivalent weight of 400g/eq, a molecular weight of 800, and a viscosity of 1400 Pa.s (E-type viscometer, 25 ℃ C., 1 rpm)
MX-135: the core-shell dispersed epoxy resin has an epoxy equivalent of 223g/eq, a molecular weight of 446, and a viscosity of 190 Pa.s (E-type viscometer, 25 ℃ C., 1 rpm)
EA-1010N: glycidyl ether-containing epoxy acrylate, available from Xinzhongcun chemical industries, inc., has a functional group equivalent of 267g/eq, a molecular weight of 420, and a viscosity of 550 Pa.s (type E viscometer, 25 ℃, 1 rpm).
(4) Curing agent
TMTP: the equivalent weight of the functional groups of trimethylolpropane tris (3-mercaptopropionate) and thiol is 140g/eq
PE-1: pentaerythritol-3-mercaptobutyrate (pentaerythritol tetrakis (3-mercaptobutyrate)) produced by Showa electric company, the functional equivalent of thiol was 136g/eq.
(5) Calcium carbonate white brilliant CC: calcium carbonate CaCO manufactured by Baishi industries Co 3 An average particle diameter of 50nm and a BET specific surface area of 26.0m 2 /g
White brilliant CC-R: calcium carbonate CaCO manufactured by Baishi industries Co 3 An average particle diameter of 80nm and a BET specific surface area of 18.0m 2 /g
Vigot-10: calcium carbonate CaCO manufactured by Baishi industries Co 3 An average particle diameter of 100nm and a BET specific surface area of 13.5m 2 /g
Vigot-15: calcium carbonate CaCO manufactured by Baishi industries Co 3 An average particle diameter of 150nm and a BET specific surface area of 10.0m 2 /g
W-B: calcium carbonate CaCO manufactured by Baishi industries Co 3 An average particle diameter of 3.6 μm and a BET specific surface area of 0.6m 2 /g。
(6) Silica dioxide
SP-04MS: silica manufactured by Deshan corporation (Tokuyama corporation) having an average particle diameter of 400nm
YA050C: manufactured by Admatechs, inc., silica having an average particle diameter of 50nm
RY-300: fumed silica, manufactured by AEROSIL Co., ltd., has an average particle diameter of 7nm.
(7) Preservation stabilizer
TEB: triethyl borate manufactured by tokyo chemical Co.
(8) Curing accelerator
PN-F: an amine epoxy adduct curing agent, available from Weisu Fine chemical Co.
[ evaluation of shape stability ]
The temperature of each curable resin composition obtained in examples and comparative examples was maintained at 25 ℃ (+ -2 ℃) and the viscosity (Pa.s) was measured under the measurement conditions that the measurement sample was 0.22ml and the rotational speed was 1rpm and 10rpm using an E-type viscometer (RE-85U, 3℃X R9.7 rotor, manufactured by Tokyo industries Co.);
then, based on the following equation 1, the TI value (1/10 rpm) was calculated;
(1) [ TI value (1/10 rpm) ]= [ viscosity at 1rpm measurement ]/[ viscosity at 10rpm measurement ]
Since some examples have exceeded the measurement limit, the measurement was also performed at a rotation speed of 2rpm and 20rpm, and the TI value (2/20 rpm) was calculated based on the following formula 2;
(2) [ TI value (2/20 rpm) ]= [ viscosity at 2rpm measurement ]/[ viscosity at 20rpm measurement ].
[ broken Linear ]
Each of the resin compositions obtained in examples and comparative examples was put into a 10ml syringe (PSY-10E) manufactured by Kagaku Highway Co., ltd. (Musashi Engineering, inc.), filling was performed by centrifugal defoaming using a centrifugal defoaming machine AWATON (AW-50-3) manufactured by Wt Kagaku Co., ltd. Ext> Aext> needleext> (ext> PNext> -ext> 21ext> Gext> -ext> Aext>)ext> manufacturedext> byext> Wucangext> highext> -ext> techext> Coext>.ext>,ext> Ltdext> wasext> attachedext> toext> theext> filledext> syringeext>,ext> andext> evaluationext> wasext> performedext> underext> theext> conditionsext> ofext> aext> dischargeext> pressureext> ofext> 300ext> kPaext> andext> aext> dischargeext> timeext> ofext> 0.2ext> sext>.ext> Specifically, the adhesive was dispensed using a dispensing controller (350 PC SmartSM- Ω X) manufactured by wutibet high-tech corporation, the moving height was changed from 1mm to 25mm after the discharge, the spot application was performed on the glass plate, and the height at which the adhesive was broken immediately above the discharge point was observed as a broken line (mm).
[ adhesion force ]
2 pieces of LCP test pieces (CM-529B, manufactured by ENEOS liquid crystal Co., ltd.) 100 mm. Times.25 mm. Times.2 mm thick were prepared, and the surface was gently rubbed with an ethanol-wet wipe. The resin composition was uniformly applied to the surface of the LCP test piece at a thickness of about 1 mm. The 2 test pieces were attached and pressed by 2 jigs so that the coating surfaces overlapped with each other by about 12 mm. At this time, the oozed resin composition was immediately wiped off with a wiper. The test pieces were uniformly arranged in an oven, and heat-cured at 80℃for 30 minutes to bond them. For the same resin, 2 test pieces were prepared. The tensile shear adhesive strength (measured environment: temperature 25 ℃ C./humidity 60% and tensile speed: 5 mm/min) of the obtained test piece was measured in accordance with JIS-K-6850 using a Tensilon Universal tester (UTM-5T, manufactured by TOYO BALDWIN Co.). Based on the maximum load (N) at which the test piece was broken, the adhesion area (mm) 2 ) The tensile shear adhesive strength was calculated by the following equation 3. The obtained tensile shear adhesive strength was referred to as "adhesion"; (3) [ tensile shear bond Strength (N/mm) 2 )]= [ maximum load (N)]Bonded area (mm) 2 )]。
The shape stability (TI value), the breaking strength (mm), the adhesion (tensile shear bonding strength (N/mm) 2 ) Table 2-1 to table 2-4);
Regarding TI, the case where TI is 2.0 or more was evaluated as good, the case where TI is 1.5 to 2.0 was evaluated as Δ, and the case where TI is 1.5 or less was evaluated as x.
Regarding the broken line, the case of 10mm or less was evaluated as good, the case of 10mm to 15mm was evaluated as delta, and the case of 15mm or more was evaluated as X;
regarding the adhesion force, it will be 2.0N/mm 2 The above was evaluated as good, and the ratio was 1.5 to 2.0N/mm 2 The case of (C) was evaluated as delta, and will be 1.5N/mm 2 The following cases were evaluated as x.
[ investigation of evaluation results ]
The results of the above evaluations are shown in tables 2-1 to 2-4;
in comparative examples 7 and 8 lacking calcium carbonate, the broken linearity and shape stability were poor;
on the other hand, the BET specific surface area of the composition was 5m 2 The resin compositions according to examples 1 to 9 of calcium carbonate of/g or more are excellent in at least two of shape stability, breaking linearity and adhesion, and are excellent in balance of these properties;
on the other hand, the BET specific surface area of the calcium carbonate is less than 5m 2 In comparative example 1 of/g, the desired shape stability could not be obtained;
in the case where silica is used instead of calcium carbonate (comparative examples 2 to 6), the properties are improved as compared with those of comparative examples 7 and 8, but the shape stability, the breakage and the adhesion are not improved in a well-balanced manner as in examples 1 to 9.
[ Table 1-1]
[ tables 1-2]
[ tables 1 to 3]
[ tables 1 to 4]
[ Table 2-1]
[ Table 2-2]
[ tables 2 to 3]
[ tables 2 to 4]
/>

Claims (16)

1. A curable resin composition comprising (A) a curable resin, (B) a BET specific surface area of 5m 2 Calcium carbonate of a ratio of/g or more, and (C) a curing agent.
2. The curable resin composition according to claim 1, wherein the (a) curable resin comprises: at least one resin selected from a high-viscosity curable resin having a viscosity of 100 Pa.s or more as measured at 25 ℃ and 1rpm by an E-type viscometer and a solid curable resin which is a resin solid at 25 ℃.
3. The curable resin composition according to claim 2, wherein the high-viscosity curable resin and the solid curable resin are 5 to 100 parts by mass per 100 parts by mass of the (a) curable resin.
4. The curable resin composition according to any one of claims 1 to 3, wherein the viscosity of the composition is 10 to 500 Pa.s as measured with an E-type viscometer at 25 ℃ and 1 rpm.
5. The curable resin composition according to any one of claim 1 to 4, wherein,
when the viscosity measured with an E-type viscometer at 25 ℃ and 1rpm is designated as V1 and the viscosity measured with an E-type viscometer at 25 ℃ and 10rpm is designated as V2, the ratio (V1/V2) of the viscosity V1 to the viscosity V2 of the curable resin composition is 1.5 to 6.0; or alternatively
When the viscosity measured with an E-type viscometer at 25℃and 2rpm is designated as V3 and the viscosity measured with an E-type viscometer at 25℃and 20rpm is designated as V4, the ratio (V3/V4) of the viscosity V3 to the viscosity V4 of the curable resin composition is 1.5 to 6.0.
6. The curable resin composition according to any one of claims 1 to 5, wherein the (a) curable resin comprises one or more selected from the group consisting of an epoxy resin and a compound having a (meth) acryloyl group.
7. The curable resin composition according to any one of claims 1 to 6, wherein component (A) comprises an epoxy resin.
8. The curable resin composition according to any one of claims 1 to 7, wherein the calcium carbonate (B) has a BET specific surface area of 5m 2 Above/g and 50m 2 And/g or less.
9. The curable resin composition according to any one of claims 1 to 8, wherein the (C) curing agent comprises a polythiol compound having 2 or more mercapto groups in 1 molecule.
10. The curable resin composition according to any one of claims 1 to 9, wherein the (a) curable resin is 5 to 80 parts by mass per 100 parts by mass of the nonvolatile component of the curable resin composition.
11. The curable resin composition according to any one of claims 1 to 10, wherein the calcium carbonate (B) is 3 to 80 parts by mass relative to 100 parts by mass of a nonvolatile component of the curable resin composition.
12. The curable resin composition according to claim 1 to 11, wherein the (C) curing agent is 5 to 80 parts by mass per 100 parts by mass of the nonvolatile component of the curable resin composition.
13. The curable resin composition according to any one of claims 1 to 12, which is applied by being discharged from a nozzle.
14. An adhesive comprising the curable resin composition according to any one of claims 1 to 13.
15. The adhesive according to claim 14, which is used for adhesion between constituent members of a camera module.
16. A bonding method comprising the step of discharging the curable resin composition according to any one of claims 1 to 13 from a nozzle.
CN202310191182.4A 2022-03-07 2023-03-02 Curable resin composition, adhesive, and adhesive method Pending CN116715939A (en)

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