CN112745770B - Curable composition - Google Patents

Curable composition Download PDF

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Publication number
CN112745770B
CN112745770B CN202011194805.6A CN202011194805A CN112745770B CN 112745770 B CN112745770 B CN 112745770B CN 202011194805 A CN202011194805 A CN 202011194805A CN 112745770 B CN112745770 B CN 112745770B
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curable composition
component
meth
acrylate
compound
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CN112745770A (en
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田村贤
佐藤大河
新田亚季
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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Priority claimed from JP2020170733A external-priority patent/JP7552221B2/en
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    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
    • H04N23/50—Constructional details

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Multimedia (AREA)
  • Signal Processing (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention addresses the problem of providing a curable composition having both excellent photocurability and excellent thermosetting properties. The solution is a curable composition comprising: (1) a compound having a (meth) acryloyl group, (2) an epoxy compound having 2 or more epoxy groups in 1 molecule and being solid at 25 ℃, (3) a polythiol compound having 2 or more mercapto groups in 1 molecule, (4) a photo radical generator, and (5) a latent curing agent, wherein the amount of the component (3) is 15% by weight or more and 50% by weight or less relative to the entire curable composition.

Description

Curable composition
Technical Field
The present invention relates to a curable composition.
Background
In recent years, along with the reduction in thickness of portable devices such as smartphones, camera modules (camera modules) mounted on portable devices such as smartphones have been reduced in size. In addition, even in wearable devices, mounting of camera modules is expected to be carried out, and demands for downsizing and thinning are increasing. Further, since the camera module is miniaturized, the parts to be bonded and fixed between the constituent members of the camera module are also becoming fine, and thus the camera module is very important for impact resistance upon falling. Therefore, even if the camera module receives an impact due to a drop, it is necessary to maintain adhesion even if the adhesion area between the constituent members is small, and when the adhesion area becomes small, the adhesion portion of the constituent members becomes easy to peel off, so that improvement of the adhesion strength per unit area of the adhesive is more important.
On the other hand, in order to avoid thermal damage to an image sensor or the like caused by high-temperature processing, an adhesive used for assembly of a camera module is required to have low-temperature curability, and also, from the viewpoint of improving production efficiency, performance of curing at low temperature and in a short time (low-temperature-short-time curability) is also required. From this viewpoint, as the low-temperature-short-time curable adhesive, ultraviolet curable adhesives and thermosetting epoxy resin adhesives are often used (for example, patent documents 1 and 2). However, the ultraviolet-curable adhesive is rapidly curable, and the other side has disadvantages such as curing deformation due to curing shrinkage, low adhesive strength, and failure to use for adhesion of a portion which is not exposed to light. On the other hand, thermosetting epoxy resin adhesives are low-temperature-short-time curable adhesives, but the following problems occur: in order to maintain the bonding posture during bonding, the bonded members must be fixed by a jig or a device, and the viscosity is reduced by the temperature rise due to heating, and sagging, flowing to a place other than the desired place, or the like is generated immediately before curing, which is not necessarily satisfactory.
In order to solve the above-described problems, there have been proposed adhesives of a type in which each component constituting a camera module is temporarily fixed by curing (pre-curing) by irradiation of light (ultraviolet rays or visible light) and is bonded (formally fixed) by curing (formally curing) by heat (for example, patent documents 3 and 4) in order to arrange the components with high precision.
[ Prior Art literature ]
[ Patent literature ]
[ Patent document 1] Japanese patent application laid-open No. 2004-140497
[ Patent document 2] Japanese patent application laid-open No. 2013-88525
Patent document 3 japanese patent laid-open publication No. 2009-51954
Patent document 4 japanese patent application laid-open No. 2009-79216.
Disclosure of Invention
Problems to be solved by the invention
Even when a light-curable and thermosetting adhesive such as described in patent documents 3 and 4 is used, there is a problem in that the adhesive strength is low and the temporary fixation is low, so that the component is movable in the manufacturing process. In addition, the camera module has a structure where light hardly reaches the inside of the module, and such a portion cannot be sufficiently photo-cured, and in fact, it is only heat-cured, and as a result, there is a problem that sufficient adhesive strength cannot be ensured.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a curable composition having both excellent photocurability and excellent thermosetting properties, and also excellent adhesive strength.
Means for solving the problems
The present invention which can achieve the above object is as follows;
[1] a curable composition comprising the following components (1) to (5):
(1) A compound having a (meth) acryloyl group,
(2) An epoxy compound having 2 or more epoxy groups in 1 molecule and being solid at 25℃,
(3) A polythiol compound having 2 or more mercapto groups in 1 molecule,
(4) Photoradical generator
(5) A latent curing agent, which is a curing agent,
The amount of the component (3) is 15 to 50 wt% based on the entire curable composition;
[2] the curable composition according to the above [1], wherein the component (2) comprises at least one selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, dicyclopentadiene type epoxy resins, and biphenyl type epoxy resins;
[3] The curable composition according to the above [1] or [2], wherein the component (3) comprises a polythiol compound having 2 to 6 mercapto groups in 1 molecule;
[4] The curable composition according to any one of the above [1] to [3], wherein the molar ratio of the total of the acryl groups, the methacryl groups, and the epoxy groups in the component (1) to the mercapto groups in the component (3) (the total of the acryl groups, the methacryl groups, and the epoxy groups in the component (1) to the mercapto groups in the component (3)) is 0.5 to 2.0;
[5] the curable composition according to any one of the above [1] to [4], wherein the component (5) comprises an amine-epoxy adduct-based compound and/or an amine-isocyanate adduct-based compound;
[6] an adhesive comprising the curable composition of any one of [1] to [5 ];
[7] the adhesive according to the above [6], which is used for adhesion between constituent members of a camera module;
[8] a sealant comprising the curable composition according to any one of the above [1] to [5 ];
[9] a coating agent comprising the curable composition according to any one of the above [1] to [5 ];
[10] A method for manufacturing a camera module, comprising the following steps (I) to (III):
(I) A step of positioning the first adhesive member and the second adhesive member coated with the curable composition according to any one of the above [1] to [5],
(II) a step of temporarily fixing the first adhesive member and the second adhesive member by curing the curable composition by irradiation with light, and
(III) a step of curing the curable composition by heating to fix the first adhesive member and the second adhesive member together.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a curable composition having both excellent photocurability and excellent thermosetting properties can be obtained.
Detailed Description
Curable composition
The curable composition of the present invention is characterized by comprising the following components (1) to (5):
(1) A compound having a (meth) acryloyl group,
(2) An epoxy compound having 2 or more epoxy groups in 1 molecule and being solid at 25 ℃ (hereinafter, may be simply referred to as "solid epoxy compound")
(3) A polythiol compound having 2 or more mercapto groups (-SH) in 1 molecule (hereinafter, sometimes simply referred to as "polythiol compound")
(4) Photoradical generator
(5) A latent curing agent, which is a curing agent,
The amount of the component (3) is 15 to 50 wt% based on the entire curable composition.
The components (1) to (5) may be used in combination of 1 kind or 2 or more kinds. When the curable composition of the present invention contains components other than the components (1) to (5), only 1 component may be used, or 2 or more components may be used in combination. The respective components are described below in order.
(1) Compounds having (meth) acryloyl groups
In the present invention, the compound having a (meth) acryloyl group used as the component (1) is a component that mainly plays a role in improving the adhesive strength. In the present invention, "(meth) acryl" means one or both of acryl and methacryl.
The number of (meth) acryloyl groups in 1 molecule of the compound having a (meth) acryloyl group may be 1 or more. When the compounds having a (meth) acryloyl group are a mixture, the number represents an average value per 1 molecule. In addition, when both an acryl group and a methacryl group are present in 1 molecule, the number refers to the total number of acryl groups and methacryl groups in 1 molecule. The number of (meth) acryloyl groups in 1 molecule of the compound having a (meth) acryloyl group (excluding the phosphoric acid-modified (meth) acrylate described later) is preferably 1 to 6, more preferably 2 to 6, still more preferably 2 to 4.
The molecular weight of the compound having a (meth) acryloyl group (excluding phosphoric acid-modified (meth) acrylate described later) is preferably 50 to 5000, more preferably 70 to 4000, still more preferably 100 to 2000. When the molecular weight is less than 50, the volatility is high, the odor and the handling property are not preferable, and when the molecular weight is more than 5000, the viscosity of the composition tends to be high and the coatability of the composition tends to be low. The molecular weight of 1000 or more means a weight average molecular weight, and can be measured by Gel Permeation Chromatography (GPC). Molecular weights less than 1000 may be determined using gravimetric analysis devices (e.g., ESI-MS).
Examples of the compound having a (meth) acryloyl group include the following compounds. The following compounds may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
(Compound having 1 acryl or methacryl group in 1 molecule)
Beta-carboxyethyl (meth) acrylate
Isobornyl (meth) acrylate
Octyl/decyl (meth) acrylate
Ethoxylated phenyl (meth) acrylate
EO-modified phenol (meth) acrylates
EO-modified ortho-phenylphenol (meth) acrylates
EO-modified para-cumylphenol (meth) acrylate
EO-modified nonylphenol (meth) acrylates
PO modified nonylphenol (meth) acrylate
N- (meth) acryloyloxyethyl hexahydrophthalimide
Omega-carboxy-polycaprolactone mono (meth) acrylates
Monohydroxyethyl (meth) acrylate phthalate
2-Hydroxy-3-phenoxypropyl (meth) acrylate.
In the present invention, "(meth) acrylate" means one or both of acrylate and methacrylate. In addition, "EO modification" refers to modification by addition of Ethylene Oxide (EO). The term "PO modification" means modification by addition of Propylene Oxide (PO).
(Compound having 2 (meth) acryloyl groups in 1 molecule)
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) acrylates
Polypropylene glycol di (meth) acrylate
Polyethylene glycol di (meth) acrylate
Neopentyl glycol hydroxypivalate di (meth) acrylate
Polyurethane having 2 (meth) acryl groups in 1 molecule
Polyesters having 2 (meth) acryloyl groups in 1 molecule.
(Compound having 3 or more (meth) acryloyl groups in 1 molecule)
Trimethylolpropane tri (meth) acrylate
PO modified trimethylolpropane tri (meth) acrylate
EO-modified trimethylolpropane tri (meth) acrylate
EO-modified isocyanuric (tri) (meth) acrylate
Pentaerythritol (tri/tetra) (meth) acrylate
Glycerol propoxylate tri (meth) acrylate
Pentaerythritol ethoxy tetra (meth) acrylate
Di (trimethylolpropane) tetra (meth) acrylate
Dipentaerythritol (penta/hexa) (meth) acrylate
Dipentaerythritol hexa (meth) acrylate
EO-modified diglycerol tetra (meth) acrylates
Polyurethane having 3 or more (meth) acryloyl groups in 1 molecule
Polyesters having 3 or more (meth) acryloyl groups in 1 molecule.
In addition, pentaerythritol (tri/tetra) (meth) acrylate is a mixture of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. The mixing ratio (pentaerythritol tri (meth) acrylate/pentaerythritol tetra (meth) acrylate) is preferably 5/95 to 95/5, more preferably 30/70 to 70/30 by weight.
In addition, dipentaerythritol (penta/hexa) (meth) acrylate is a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. The mixing ratio (dipentaerythritol penta (meth) acrylate/dipentaerythritol hexa (meth) acrylate) is preferably 5/95 to 95/5 by weight, more preferably 30/70 to 70/30.
In addition, as the compound having a (meth) acryloyl group, EO-modified isocyanuric acid (di/tri) (meth) acrylate may be used. Here, the EO-modified isocyanuric acid (di/tri) (meth) acrylate is a mixture of EO-modified isocyanuric acid di (meth) acrylate and EO-modified isocyanuric acid tri (meth) acrylate. The mixing ratio (EO-modified di (meth) isocyanurate acrylate/EO-modified tri (meth) isocyanurate acrylate) is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, still more preferably 40/60 to 60/40, by weight.
From the viewpoints of storage stability and adhesion, the component (1) preferably contains a phosphoric acid-modified (meth) acrylate. Here, "phosphoric acid modified" means modified by an ester bond with phosphoric acid. The phosphoric acid modified (meth) acrylate may be used in an amount of 1 or 2 or more. The phosphoric acid-modified (meth) acrylate is preferably a phosphoric acid-modified methacrylate.
The phosphoric acid modified (meth) acrylate can be produced by, for example, the following method (i), but the present invention is not limited to this method,
(I) A method of reacting a compound having a (meth) acryloyl group and a hydroxyl group with phosphoric acid.
The compound having a (meth) acryloyl group and a hydroxyl group in 1 molecule which can be used in the above-mentioned method (i) can be produced by, for example, the following method (ii) or (iii), but the present invention is not limited to these methods,
(Ii) A method of reacting (meth) acrylic acid or (meth) acrylic acid ester with a polyol (for example, alkylene glycol, glycerol, etc.) in such an amount ratio that the hydroxyl groups of the polyol remain;
(iii) A method of adding an alkylene oxide (e.g., ethylene oxide, propylene oxide, etc.) to (meth) acrylic acid.
As the phosphoric acid-modified (meth) acrylate, commercially available ones can be used. Examples of such commercial products include "EBECRYL168" manufactured by ALLNEX, japan chemical Co., ltd., and "KAYAMER PM-2" and "KAYAMER PM-21" manufactured by Kagaku chemical Co., ltd., and "LIGHT ESTER P-1M" and "LIGHT ESTER P-2M" and "LIGHT ACRYLATE P-1A (N)" manufactured by North chemical Co., ltd.).
The number of (meth) acryloyl groups in 1 molecule of the phosphoric acid-modified (meth) acrylate is preferably 0.5 to 3, more preferably 1 to 2, still more preferably 1 to 1.5. When the phosphoric acid-modified (meth) acrylate is a mixture, the number represents an average value per 1 molecule.
The molecular weight of the phosphoric acid-modified (meth) acrylate is preferably 100 to 1000, more preferably 150 to 800, still more preferably 200 to 600.
When the phosphoric acid-modified (meth) acrylate is used, the amount thereof is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, still more preferably 0.05 to 2 parts by weight per 100 parts by weight of the component (1) from the viewpoints of storage stability and curability.
In one embodiment of the present invention, the component (1) preferably contains at least one selected from tricyclodecanedimethanol di (meth) acrylate, EO-modified bisphenol a di (meth) acrylate, dipentaerythritol hexa (meth) acrylate and phosphoric acid-modified (meth) acrylate, more preferably at least one selected from tricyclodecanedimethanol di (meth) acrylate, EO-modified bisphenol a di (meth) acrylate, dipentaerythritol hexa (meth) acrylate and phosphoric acid-modified (meth) acrylate.
In another embodiment of the present invention, the component (1) preferably contains a mixture of phosphoric acid-modified (meth) acrylate and at least one selected from tricyclodecane dimethanol di (meth) acrylate, EO-modified bisphenol a di (meth) acrylate and dipentaerythritol hexa (meth) acrylate, more preferably a mixture of phosphoric acid-modified (meth) acrylate and at least one selected from tricyclodecane dimethanol di (meth) acrylate, EO-modified bisphenol a di (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
In another embodiment of the present invention, the component (1) is preferably a mixture comprising "tricyclodecanedimethanol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate or dipentaerythritol hexa (meth) acrylate" and "phosphoric acid-modified (meth) acrylate", more preferably a mixture of "tricyclodecanedimethanol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate or dipentaerythritol hexa (meth) acrylate" and "phosphoric acid-modified (meth) acrylate".
The amount of the component (1) is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, still more preferably 60% by weight or less, still more preferably 55% by weight or less, still more preferably 50% by weight or less, based on the entire curable composition, from the viewpoint of curability and adhesiveness.
(2) Solid epoxy Compound
The component (2) used in the present invention is not particularly limited as long as it is a compound having 2 or more epoxy groups in 1 molecule and being solid at 25 ℃.
Examples of the solid epoxy compound include epoxy resins which have 2 or more epoxy groups in1 molecule and are solid at 25 ℃. The epoxy resin as a monomer (i.e., a monomeric epoxy resin) may be used as the component (2) of the present invention as long as it has 2 or more epoxy groups in1 molecule and is solid at 25 ℃.
Examples of the epoxy resin include bisphenol a type epoxy resin, hydrogenated bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy resin, aromatic glycidylamine type epoxy resin, alicyclic epoxy resin, oxazolidone ring type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol a novolak type epoxy resin, and the like. The epoxy resin may be used in an amount of 1 or 2 or more.
The epoxy equivalent of the component (2) (i.e., the solid epoxy compound) is preferably 50 to 5000g/eq, more preferably 100 to 3000g/eq, still more preferably 150 to 1000g/eq, from the viewpoint of reactivity and the like. The epoxy equivalent herein means the gram number (unit: g/eq) of the compound containing 1 gram equivalent of epoxy group. In other words, the epoxy equivalent means a value obtained by dividing the molecular weight of a compound containing an epoxy group by the number of epoxy groups the compound has, i.e., the molecular weight per 1 epoxy group. The epoxy equivalent was measured according to the method specified in JIS K7236.
In one embodiment of the present invention, the component (2) preferably contains at least one selected from the group consisting of bisphenol a type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin, and more preferably at least one selected from the group consisting of bisphenol a type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin. In this embodiment, bisphenol a type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin each have 2 or more epoxy groups in 1 molecule and are solid at 25 ℃.
In another embodiment of the present invention, the component (2) preferably contains a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a dicyclopentadiene type epoxy resin, or a biphenyl type epoxy resin, more preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a dicyclopentadiene type epoxy resin, or a biphenyl type epoxy resin. In this embodiment, bisphenol a type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin each have 2 or more epoxy groups in1 molecule and are solid at 25 ℃.
In another embodiment of the present invention, the component (2) preferably contains a bisphenol a-type epoxy resin having 2 or more epoxy groups in 1 molecule and being solid at 25 ℃, more preferably contains 2 or more epoxy groups in 1 molecule and being solid at 25 ℃.
The curable composition of the present invention may contain a compound having 2 or more epoxy groups in 1 molecule and being liquid at 25 ℃ (hereinafter, may be simply referred to as "liquid epoxy compound"). However, from the viewpoint of the effects of the present invention (i.e., excellent photocurability and excellent thermosetting properties), the curable composition of the present invention preferably contains no liquid epoxy compound or contains a liquid epoxy compound in an amount of 20 parts by weight or less per 100 parts by weight of component (2) (i.e., solid epoxy compound). The amount of the liquid epoxy compound is preferably 10 parts by weight or less, more preferably 5 parts by weight or less per 100 parts by weight of the component (2). In particular, the curable composition of the present invention preferably does not contain a liquid epoxy compound.
The amount of the component (2) is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, still more preferably 70% by weight or less, still more preferably 60% by weight or less, still more preferably 55% by weight or less, based on the entire curable composition, from the viewpoint of curability and handleability of the curable composition.
(3) Polythiol Compound
In the present invention, "polythiol compound having 2 or more mercapto groups in 1 molecule" used as component (3) mainly functions as a curing agent that reacts with component (1) by irradiation with light such as ultraviolet light to cure the composition. The number of mercapto groups in 1 molecule of the polythiol compound is preferably 2 to 6, more preferably 3 to 6, still more preferably 3 to 5, particularly preferably 3 or 4.
The polythiol compound may be commercially available, or may be produced by a known method (for example, the method described in Japanese patent application laid-open No. 2012-153794 or International publication No. 2001/00698).
Examples of the polythiol compound include partial esters of a polyhydric alcohol and a mercapto organic acid, and full esters of a polyhydric alcohol and a mercapto organic acid. Here, the partial ester refers to an ester of a polyhydric alcohol and a carboxylic acid, and is an ester in which an ester bond is formed as a part of the hydroxyl group of the polyhydric alcohol; full esters refer to esters in which the hydroxyl groups of the polyol all form ester linkages.
Examples of the polyhydric alcohol include ethylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like.
Examples of the mercaptoorganic acid include mercaptoaliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid (for example, 3-mercaptopropionic acid) and mercaptobutyric acid (for example, 3-mercaptobutyric acid and 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); mercaptoaromatic monocarboxylic acids such as mercaptobenzoic acid (e.g., 4-mercaptobenzoic acid). The number of carbon atoms of the mercapto aliphatic monocarboxylic acid is preferably 2 to 8, more preferably 2 to 6, still more preferably 2 to 4, particularly preferably 3. Among the above mercapto organic acids, the mercapto aliphatic monocarboxylic acid having 2 to 8 carbon atoms is 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 (mercaptoacetic acid) ester, trimethylolethane bis (3-mercaptopropionic acid) ester, trimethylolethane bis (3-mercaptobutyric acid) ester, trimethylolethane bis (4-mercaptobutyric acid) ester, trimethylolpropane bis (mercaptoacetic acid) ester, trimethylolpropane bis (3-mercaptopropionic acid) ester, trimethylolpropane bis (3-mercaptobutyric acid) ester, trimethylolpropane bis (4-mercaptobutyric acid) ester, pentaerythritol tris (mercaptoacetic acid) ester, pentaerythritol tris (3-mercaptopropionic acid) ester, pentaerythritol tris (3-mercaptobutyric acid) ester, pentaerythritol tris (4-mercaptobutyric acid) ester, dipentaerythritol tetrakis (mercaptoacetic acid) ester, dipentaerythritol tetrakis (3-mercaptopropionic acid) ester, dipentaerythritol tetrakis (3-mercaptobutyric acid) ester, dipentaerythritol tetrakis (4-mercaptobutyric acid) ester, and the like.
Specific examples of the full ester of the polyhydric alcohol and the mercapto organic acid include: ethylene glycol bis (mercaptoacetic acid) ester, ethylene glycol bis (3-mercaptopropionic acid) ester, ethylene glycol bis (3-mercaptobutyric acid) ester, ethylene glycol bis (4-mercaptobutyric acid) ester, trimethylolethane tris (mercaptoacetic acid) ester, trimethylolethane tris (3-mercaptopropionic acid) ester, trimethylolethane tris (3-mercaptobutyric acid) ester, trimethylolethane tris (4-mercaptobutyric acid) ester, trimethylolpropane tris (mercaptoacetic acid) ester, trimethylolpropane tris (3-mercaptopropionic acid) ester, trimethylolpropane tris (3-mercaptobutyric acid) ester, trimethylolpropane tris (4-mercaptobutyric acid) ester, pentaerythritol tetrakis (mercaptoacetic acid) ester, pentaerythritol tetrakis (3-mercaptopropionic acid) ester, pentaerythritol tetrakis (4-mercaptobutyric acid) ester, dipentaerythritol hexa (mercaptoacetic acid) ester, dipentaerythritol hexa (3-mercaptopropionic acid) ester, dipentaerythritol hexa (3-mercaptobutyric acid) ester, dipentaerythritol hexa (4-mercaptobutyric acid) ester, etc.
From the viewpoint of storage stability, the partial ester and the full ester are preferably those having an extremely small amount of alkaline impurities, and more preferably those which do not require the use of alkaline substances for production.
Further, as the component (3), an alkane polythiol compound such as1, 4-butanedithiol, 1, 6-hexanedithiol, 1, 10-decanedithiol, etc. may be used; polyethers containing terminal mercapto groups, and the like; polythioethers containing terminal mercapto groups, and the like; a polythiol compound obtained by reacting an epoxy compound with hydrogen sulfide; a polythiol compound produced by using an alkaline substance as a reaction catalyst in the production process of the polythiol compound, such as a polythiol compound having a terminal mercapto group obtained by reacting a polythiol compound with an epoxy compound. The polythiol compound produced using the alkaline substance is preferably used after dealkalization treatment to make the alkali metal (alkali metal) ion concentration 50 weight ppm or less.
As the dealkalization treatment of the polythiol compound produced using the alkaline substance, for example, a method in which the polythiol compound is dissolved in an organic solvent such as acetone or methanol, and an acid such as dilute hydrochloric acid or dilute sulfuric acid is added to neutralize the polythiol compound, and then the obtained product is desalted by extraction or washing; a method of adsorption using an ion exchange resin; methods of purification by distillation, and the like, but are not limited to these methods.
As the component (3), for example, may be used: tris [ (3-mercaptopropionyloxy) ethyl ] isocyanurate, 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutyryloxy) ethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, tris (3-mercaptopropyl) isocyanurate, bis (3-mercaptopropyl) isocyanurate, 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril, 4' -isopropylidenediphenyl bis (3-mercaptopropyl) ether, and the like.
Component (3) preferably contains a polythiol compound having 2 to 6, more preferably 3 to 6, still more preferably 3 to 5, particularly preferably 3 or 4 mercapto groups in 1 molecule.
In one embodiment of the present invention, the component (3) preferably contains at least one member selected from pentaerythritol tetrakis (3-mercaptopropionic acid) ester, pentaerythritol tetrakis (3-mercaptobutyric acid) ester, tris (3-mercaptopropyl) isocyanurate, trimethylolpropane tris (3-mercaptopropionic acid) ester, dipentaerythritol hexa (3-mercaptopropionic acid) ester, tris [ (3-mercaptopropionyloxy) ethyl ] isocyanurate, ethylene glycol bis (mercaptoacetic acid) ester, trimethylolpropane tris (mercaptoacetic acid) ester, pentaerythritol tetrakis (mercaptoacetic acid) ester, 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutyryloxy ethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyric acid) ester, trimethylolethane tris (3-mercaptobutyric acid) ester, 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril, 4' -isopropylidene) and pentaerythritol tetrakis (3-mercaptopropyl) ether.
In another embodiment of the present invention, component (3) preferably contains pentaerythritol tetrakis (3-mercaptopropionic acid) ester, pentaerythritol tetrakis (3-mercaptobutyric acid) ester or tris (3-mercaptopropyl) isocyanurate, more preferably pentaerythritol tetrakis (3-mercaptopropionic acid) ester, pentaerythritol tetrakis (3-mercaptobutyric acid) ester or tris (3-mercaptopropyl) isocyanurate, and still more preferably pentaerythritol tetrakis (3-mercaptopropionic acid) ester.
From the viewpoint of curability, the molar ratio of the total of the acryl groups, methacryl groups, and epoxy groups in component (1) to the mercapto groups in component (3) (the total of the acryl groups, methacryl groups, and epoxy groups in component (2)/the mercapto groups in component (3)) is preferably from 0.5 to 2.0, more preferably from 0.6 to 1.6, even more preferably from 0.7 to 1.5, and particularly preferably from 0.8 to 1.3.
From the viewpoint of curability and adhesion, the amount of component (3) is required to be 15% by weight or more and 50% by weight or less relative to the entire curable composition. The amount of the component (3) is preferably 20% by weight or more, more preferably 25% by weight or more, still more preferably 45% by weight or less, and still more preferably 40% by weight or less, based on the entire curable composition.
From the viewpoint of the handleability of the curable composition, the total amount of the components (1) and (3) is preferably 50 parts by weight or more, more preferably 60 parts by weight or more, and even more preferably 70 parts by weight or more per 100 parts by weight of the component (2). On the other hand, from the viewpoint of adhesion, the total amount of the components (1) and (3) is preferably 2000 parts by weight or less, more preferably 1500 parts by weight or less, and still more preferably 1000 parts by weight or less per 100 parts by weight of the component (2).
(4) Photo radical generator
In the present invention, the photoradical generator used as the component (4) is not particularly limited. Examples of the photo radical generator include: a phenylalkyl ketone (alkylphenone) type photoradical generator, an acyl phosphine oxide type photoradical generator, an oxime ester type photoradical generator, an α -hydroxy ketone type photoradical generator, and the like. The photoradical generator is preferably a phenylalkyl ketone photoradical generator.
Examples of the phenylalkylketone photo-radical generator include: 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] - [4- (4-morpholino) phenyl ] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2-diethoxyacetophenone, 2, 4-diethylthioxanthone, diphenyl- (2, 4, 6-trimethylbenzoyl) phosphine oxide, (2, 4, 6-trimethylbenzoyl) phenylphosphinate ethyl ester, 4' -bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenyl ketone, 2-dimethoxy-1, 2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-propenyl) -1-isopropyl-2-methyl-1-one, and the like.
Examples of the acylphosphine oxide-based photo-radical generator include: 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, and the like.
Examples of the oxime ester-based photo-radical generator include: 1- [4- (phenylsulfanyl) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime), 1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone O-acetyl oxime, and the like.
Examples of the α -hydroxyketone photo-radical generator include: benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexyl phenyl ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, and the like.
Examples of commercial products of the photoradical generator include: "Irgacure 1173" (2-hydroxy-2-methyl-1-phenylpropane-1-one), "Irgacure OXE01" (1- [4- (phenylsulfanyl) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime)), "Irgacure OXE02" (1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone O-acetoxime), IGM RESINS B.V. company "Esacuure KTO 46" (2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, a mixture of oligo [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propane ] and a methylbenzophenone derivative), "Esacure KIP 150" (oligomer of 2-hydroxy-1- (4-isopropenylphenyl) -2-methylpropan-1-one), and the like.
The amount of the component (4) is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, and even more preferably 0.1% by weight or more, based on the entire curable composition, from the viewpoint of obtaining a curable composition that can be effectively photo-cured upon irradiation with light. On the other hand, the amount of the component (4) is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 2% by weight or less, based on the entire curable composition, from the viewpoint of suppressing outgas (outgas) due to the photo-radical generator or its decomposition product remaining in the cured product.
(5) Latent curing agent
In the present invention, the latent curing agent used as the component (5) is an additive known in the art of epoxy resins and the like, which does not cure epoxy resins and the like at ordinary temperature (25 ℃) but cures epoxy resins and the like by heating.
Examples of the latent curing agent include: imidazole compounds which are solid at ordinary temperature, amine-epoxy adduct-based compounds (reaction products of amine compounds and epoxy compounds), amine-isocyanate adduct-based compounds (reaction products of amine compounds and isocyanate compounds), and the like.
Examples of the imidazole compound that is solid at normal 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- (2-methyl-1-imidazolyl) ethyl ] -1,3, 5-triazine/isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazotrimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, N- (2-methylimidazole-1-ethyl) urea, and the like.
Examples of the epoxy compound used as a raw material of the amine-epoxy adduct-based compound 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; glycidylamine compound obtained by reacting epichlorohydrin with 4,4' -diaminodiphenylmethane, m-aminophenol or the like; and a polyfunctional epoxy compound such as an epoxidized phenol novolac resin, an epoxidized cresol novolac resin, or an epoxidized polyolefin, or a monofunctional epoxy compound such as butyl glycidyl ether, phenyl glycidyl ether, or glycidyl methacrylate; etc.
The amine compound used as a raw material of the amine-epoxy adduct-based compound or the amine-isocyanate adduct-based compound may be any compound having 1 or more active hydrogen atoms capable of undergoing an addition reaction with an epoxy group or an isocyanate group (alias: isocyanate group) in 1 molecule and having 1 or more amino groups (at least one of a primary amino group, a secondary amino group, and a tertiary amino group) in 1 molecule. Examples of such amine compounds include: aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4' -diaminodicyclohexylmethane; aromatic amine compounds such as 4,4' -diaminodiphenylmethane and 2-methylaniline; heterocyclic compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2, 4-dimethylimidazoline, piperidine and piperazine; etc.
In addition, if a compound having a tertiary amino group is used, an excellent latent curing agent can be produced. Examples of the compound having a tertiary amino group include: amines having a tertiary amino group such as dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, 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-dimethylpyridine, N-nicotinic acid, N-dimethylpyridine, nicotinic acid, N-dimethylhydrazine, nicotinic acid, N-methylhydrazine, nicotinic acid, and the like, alcohols having tertiary amino groups such as N, N-dimethylpropionyl hydrazide, nicotinic hydrazide, isonicotinyl hydrazide (isonicotinyl hydrazine), phenols, thiols, carboxylic acids, and hydrazides; etc.
In the case of producing an amine-epoxy adduct compound by subjecting an epoxy compound and an amine compound to an addition reaction, an active hydrogen compound having 2 or more active hydrogens in 1 molecule may be further added. Examples of such active hydrogen compounds include: polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resins, polyhydric alcohols such as trimethylolpropane, polycarboxylic acids such as adipic acid, and phthalic acid, 1, 2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, thioglycolic acid, anthranilic acid, and lactic acid.
Examples of the isocyanate compound used as a raw material of the amine-isocyanate adduct-based compound include: monofunctional isocyanate compounds such as butyl isocyanate, isopropyl isocyanate, phenyl isocyanate and benzyl isocyanate; 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 (xylylene diisocyanate), p-phenylene diisocyanate, 1,3, 6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and a terminal isocyanate group-containing compound obtained by the reaction of these polyfunctional isocyanate compounds with an active hydrogen compound; etc. Examples of such a terminal isocyanate group-containing compound include: an addition compound having a terminal isocyanate group obtained by reacting toluene diisocyanate with trimethylolpropane, an addition compound having a terminal isocyanate group obtained by reacting toluene diisocyanate with pentaerythritol, and the like.
The latent curing agent can be easily obtained, for example, by the following method: the above raw materials are mixed appropriately, reacted at a temperature of 20 to 200 ℃, cooled to solidify, and then pulverized, or reacted in a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc., and then the solid component is pulverized after desolvation.
As the latent curing agent, commercially available ones can be used. Examples of commercial products of amine-epoxy adduct compounds include: "Ajicure PN-23", "Ajicure PN-40", "Ajicure PN-50", "Ajicure PN-H", manufactured by Ajinomoto Fine chemical Co., inc. "Harden X-3661S", "Harden X-3670S", manufactured by A.C.R. Co., ltd., "NOVACURE HX-3742", "NOVACURE HX-3721", manufactured by Asahi Kabushiki Kaisha. Examples of commercial products of amine-isocyanate adduct compounds include: manufactured by Kagaku Co., ltd. T & K TOKA "Fujicure FXR-1000"、"Fujicure FXR-1030"、"Fujicure FXR-1020"、"Fujicure FXR-1030"、"Fujicure FXR-1081"、"Fujicure FXR-1121".
The component (5) preferably contains an amine-epoxy adduct-based compound and/or an amine-isocyanate adduct-based compound, more preferably an amine-epoxy adduct-based compound and/or an amine-isocyanate adduct-based compound, still more preferably an amine-epoxy adduct-based compound or an amine-isocyanate adduct-based compound, particularly preferably an amine-epoxy adduct-based compound.
The amount of the component (5) is preferably 1% by weight or more, more preferably 2% by weight or more, and still more preferably 3% by weight or more, based on the entire curable composition, from the viewpoint of curability due to heat. The amount of the component (5) is preferably 20% by weight or less, more preferably 15% by weight or less, and still more preferably 10% by weight or less, based on the entire curable composition, from the viewpoint of storage stability.
Stabilizer (6)
The curable composition of the present invention may further contain a stabilizer as component (6) from the viewpoint of storage stability and the like. Examples of the stabilizer include boric acid ester compounds, titanate compounds, aluminate compounds, zirconate compounds, and isocyanate compounds.
As described above, the phosphoric acid modified (meth) acrylate of 1 kind as the component (1) has a function of improving the storage stability of the curable composition. Therefore, from the viewpoint of storage stability, the curable composition of the present invention preferably contains a phosphoric acid modified (meth) acrylate as component (1) and/or contains a stabilizer as component (6).
Examples of the borate compound include: trimethyl borate, triethyl borate, 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) borane, tribenzyl borate, triphenyl borate, triortholyl borate, tricresyl borate, triethanolamine borate, and the like.
Examples of the titanate compound include: tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraoctyl titanate, and the like.
Examples of the aluminate compound include: triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, trioctyl aluminate, and the like.
Examples of the zirconate compound include: tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, tetrabutyl zirconate, and the like.
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, 2, 4-toluene diisocyanate, tolylene diisocyanate (toluylene diisocyanate), 2, 6-toluene diisocyanate, 1, 5-naphthalene diisocyanate, diphenylmethane-4, 4' -diisocyanate, dimethylbiphenyl diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, bicycloheptane triisocyanate and the like.
The stabilizer is preferably a borate compound, more preferably triethyl borate, tri-n-propyl borate, triisopropyl borate and tri-n-butyl borate, and even more preferably triethyl borate, from the viewpoint of versatility of the stabilizer and storage stability of the curable composition.
When component (6) is used, the amount is not particularly limited, but from the viewpoint of storage stability, the amount is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, still more preferably 0.1% by weight or more, still more preferably 5% by weight or less, still more preferably 3% by weight or less, and still more preferably 2% by weight or less, relative to the entire curable composition.
In a preferred embodiment of the present invention, the curable composition of the present invention contains at least one selected from tricyclodecane dimethanol di (meth) acrylate, EO-modified bisphenol a di (meth) acrylate and dipentaerythritol hexa (meth) acrylate as component (1), and the curable composition of the present invention contains phosphoric acid-modified (meth) acrylate as component (1) and/or contains a stabilizer as component (6). In this embodiment, the stabilizer is preferably a borate compound, more preferably at least one selected from the group consisting of triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate, and still more preferably triethyl borate.
In another preferred embodiment of the present invention, the component (1) is a mixture of phosphoric acid-modified (meth) acrylate and at least one selected from tricyclodecane dimethanol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
In another preferred embodiment of the present invention, the component (1) is at least one selected from tricyclodecane dimethanol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and the curable composition of the present invention contains a stabilizer as the component (6). In this embodiment, the stabilizer is preferably a borate compound, more preferably at least one selected from the group consisting of triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate, and still more preferably triethyl borate.
In another preferred embodiment of the present invention, the component (1) is a mixture of phosphoric acid-modified (meth) acrylate and at least one selected from tricyclodecane dimethanol di (meth) acrylate, EO-modified bisphenol a di (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and the curable composition of the present invention contains a stabilizer as the component (6). In this embodiment, the stabilizer is preferably a borate compound, more preferably at least one selected from the group consisting of triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate, and still more preferably triethyl borate.
In another preferred embodiment of the present invention, the curable composition of the present invention contains tricyclodecanedimethanol di (meth) acrylate, EO-modified bisphenol a di (meth) acrylate or dipentaerythritol hexa (meth) acrylate as component (1), and the curable composition of the present invention contains phosphoric acid-modified (meth) acrylate as component (1) and/or contains a stabilizer as component (6). In this embodiment, the stabilizer is preferably a borate compound, more preferably at least one selected from the group consisting of triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate, and still more preferably triethyl borate.
In another preferred mode of the invention, component (1) is a mixture of "tricyclodecanedimethanol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate or dipentaerythritol hexa (meth) acrylate" with "phosphoric acid modified (meth) acrylate".
In another preferred embodiment of the present invention, the component (1) is tricyclodecane dimethanol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate or dipentaerythritol hexa (meth) acrylate, and the curable composition of the present invention contains a stabilizer as the component (6). In this embodiment, the stabilizer is preferably a borate compound, more preferably at least one selected from the group consisting of triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate, and still more preferably triethyl borate.
In another preferred mode of the present invention, the component (1) is a mixture of "tricyclodecanedimethanol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate or dipentaerythritol hexa (meth) acrylate" and "phosphoric acid-modified (meth) acrylate", and the curable composition of the present invention contains a stabilizer as the component (6). In this embodiment, the stabilizer is preferably a borate compound, more preferably at least one selected from the group consisting of triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate, and still more preferably triethyl borate.
< Other Components >)
The curable composition of the present invention may contain other components than the above components within a range that does not impair the effects of the present invention. Examples of the other component include a polymerization inhibitor (e.g., dibutylhydroxytoluene, barbituric acid); an antioxidant; inorganic fillers (e.g., calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (aluminum oxide), zinc oxide, silica, potassium titanate, kaolin, talc, quartz powder, etc.); an organic filler comprising a copolymer obtained by copolymerizing "polymethyl methacrylate and/or polystyrene" with "a monomer copolymerizable with the monomers constituting them"; a thixotropic agent; a defoaming agent; a leveling agent; a coupling agent; a flame retardant; a pigment; a dye; fluorescent agents, and the like. The other components may be used in an amount of 1 or 2 or more.
Production and curing of curable composition
The curable composition of the present invention can be prepared as a one-component curable composition by uniformly mixing the components using, for example, a kneader, a mixer, a three-roll mill, or the like. The temperature of the curable composition at the time of mixing is usually 10 to 50 ℃, preferably 20 to 40 ℃.
The light to be irradiated when the curable composition of the present invention is cured by light is preferably ultraviolet light. The peak wavelength of the irradiated light is preferably 300 to 500nm. The illuminance of the irradiated light is preferably 100 to 5000mW/cm 2, more preferably 300 to 4000mW/cm 2. The exposure amount is preferably 500 to 3000mJ/cm 2, more preferably 1000 to 3000mJ/cm 2.
Examples of the light irradiation device include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an excimer laser, a chemical lamp (CHEMICAL LAMP), a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, a sodium lamp, a fluorescent lamp, an LED-type SPOT-type UV irradiator, a xenon lamp, and a DEEP UV lamp.
The heating temperature at the time of thermosetting the curable composition of the present invention is not particularly limited, and is, for example, 50 to 150 ℃, preferably 60 to 100 ℃. The curable composition of the present invention is excellent in low-temperature curability and exhibits excellent thermosetting properties even at a low curing temperature of 100 ℃ or less. The heating time for heat curing the curable composition of the present invention is not particularly limited, and is, for example, 10 to 120 minutes, preferably 30 to 60 minutes.
Use of curable composition
The curable composition of the present invention has both excellent photocurability and excellent thermosetting properties, and can form a cured product having high adhesive strength, and therefore can be used for adhesives, sealants, coating agents, and the like. Accordingly, the present invention also provides an adhesive, a sealant and a coating agent comprising the curable composition. The adhesive is preferably used for bonding the constituent members of the camera module.
Method for manufacturing camera module
The present invention provides a method for manufacturing a camera module, comprising the following steps (I) to (III):
(I) A step of positioning a first adhesive member and a second adhesive member coated with the curable composition of the present invention;
(II) a step of temporarily fixing the first adhesive member and the second adhesive member by curing the curable composition by irradiation with light; and
(III) a step of curing the curable composition by heating to fix the first adhesive member and the second adhesive member together. Here, the first adhesive member refers to a member coated with the curable composition of the present invention, and the second adhesive member refers to another member adhered to the first adhesive member. The second adhesive member may be coated with the curable composition of the present invention or may not be coated with the curable composition of the present invention.
According to the manufacturing method of the present invention, the components can be positioned with high accuracy, and the first adhesive member and the second adhesive member can be bonded with high adhesive strength, and as a result, a high-quality camera module can be manufactured with high efficiency.
In the step (II), due to the relationship between the arrangement positions of the first adhesive member and the second adhesive member, there may be a case where an unirradiated portion where light is not irradiated to the applied curable composition remains. However, since the curable composition of the present invention has good thermosetting properties, the non-irradiated portion is sufficiently cured by the thermosetting in the step (III), and the final curing is achieved, whereby a cured product having high adhesive strength can be formed from the entire curable composition to be applied.
The light irradiation conditions in step (II) and the heating conditions in step (III) in the method for manufacturing a camera module of the present invention are as described above.
Examples
Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.
1. Raw materials
< Component (1): compounds having (meth) acryloyl groups
(1A) IRR-214K: DAICEL-ALLNEX, tricyclodecane dimethanol diacrylate, molecular weight: number of acryl groups in 300,1 molecules: 2
(1B) EBECRYL150: EO-modified bisphenol A diacrylate, molecular weight: number of acryl groups in 512,1 molecules: 2
(1C) DPHA: dipentaerythritol hexaacrylate, manufactured by DAICEL-ALLNEX, inc., molecular weight: number of acryl groups in 524,1 molecules: 6
(1D) EBECRYL168: phosphoric acid modified methacrylate, manufactured by DAICEL-ALLNEX company, molecular weight: number of methacryloyl groups in 270,1 molecules: 1.5.
< Component (2): solid epoxy Compound
(2A) jER1001: bisphenol A type epoxy resin, epoxy Equivalent (EPW) manufactured by Mitsubishi chemical corporation: 475g/eq, softening point: 64 ℃, number of epoxy groups in 1 molecule: 2
(2B) jER4005P: bisphenol F type epoxy resin, epoxy Equivalent (EPW) manufactured by Mitsubishi chemical corporation: 538g/eq, softening point: 87 ℃, number of epoxy groups in 1 molecule: 2
(2C) HP-7200: dicyclopentadiene type epoxy resin, epoxy Equivalent (EPW) manufactured by DIC corporation: 258g/eq, softening point: 56-66 ℃, number of epoxy groups in 1 molecule: 2 to 3
(2D) YX4000H: biphenyl type epoxy resin, epoxy Equivalent (EPW) manufactured by mitsubishi chemical company: 192 g/eq), melting point: 105 ℃, number of epoxy groups in 1 molecule: 2.
< Ingredient (2'): liquid epoxy Compound
(2' A) EX-211: neopentyl glycol diglycidyl ether, manufactured by Nagase ChemteX corporation, epoxy Equivalent (EPW): 138g/eq, liquid at 25 ℃, number of epoxide groups in 1 molecule: 2
(2' B) jER828EL: bisphenol A type epoxy resin, epoxy Equivalent (EPW) manufactured by Mitsubishi chemical corporation: 190g/eq, liquid at 25 ℃,1 number of epoxide groups in the molecule: 2
(2' C) EXA-4816: aliphatic modified bisphenol A type epoxy resin, manufactured by DIC Co., ltd., epoxy Equivalent (EPW): 403g/eq, liquid at 25 ℃,1 number of epoxy groups in the molecule: 2
(2'D) BF-1000: epoxidised 1, 2-polybutadiene, epoxy Equivalent (EPW) manufactured by ADEKA corporation: 210g/eq, liquid at 25 ℃,1 number of epoxy groups in the molecule: 5.
< Component (3): polythiol Compounds >
(3A) PEMP: SC organic chemical company, pentaerythritol tetrakis (3-mercaptopropionate), molecular weight: number of mercapto groups in 489,1 molecules: 4
(3B) PE1: "Karenz MT", manufactured by Zhaowa electric company, pentaerythritol tetrakis (3-mercaptobutyrate) having a molecular weight: number of mercapto groups in 544,1 molecules: 4
(3C) TMPIC: tris (3-mercaptopropyl) isocyanurate, molecular weight: number of mercapto groups in 351,1 molecules: 3.
< Component (4): photo radical generator >)
(4A) Irgacure 1173: BASF Co., ltd., 2-hydroxy-2-methyl-1-phenylpropane-1-one
(4B) Esacure KIP 150: IGM RESINS b.v. oligomers of 2-hydroxy-1- (4-isopropenylphenyl) -2-methylpropan-1-one.
< Ingredient (5): latent curing agent >
(5A) PN-23: amine-epoxy adduct-based compound manufactured by Weisu Fine chemical Co., ltd
(5B) FXR1081: amine-isocyanate adduct-based compound (T & K TOKA).
< Ingredient (6): stabilizer >
(6A) Triethyl borate: manufactured by tokyo chemical industry co.
2. Evaluation test
< Determination of adhesive Strength >
(1) Measurement of adhesive Strength 1 after photo-curing
A curable composition was applied to a Liquid Crystal Polymer (LCP) plate (CM-301B manufactured by JX Nitshi energy Co., ltd.) having a thickness of 100mm X25 mm X2 mm in an amount of 1 to 3mg, a chip capacitor (JIS designation 2012 size) was placed thereon, and the cured product was subjected to photo-curing under the following conditions, and the adhesive strength 1 of the cured product was measured and evaluated on the following basis.
(2) Determination of bond Strength 2 after light and Heat curing
As described above, the curable composition was applied to the LCP board and the chip capacitor was placed, and the resultant was subjected to the above operations, followed by measurement of the adhesive strength 2 of the cured product under the following conditions by irradiation with light and heat, and evaluation was performed on the basis of the following criteria.
(3) Measurement of adhesive Strength 3 after Heat curing
As described above, the curable composition was applied to the LCP board and the chip capacitor was placed, and the resultant was thermally cured under the following conditions, and the adhesive strength 3 of the cured product was measured and evaluated on the following basis.
For adhesive strength, the chip capacitor was broken from the lateral direction by a push-pull tester (bond tester) (Dega series 4000), and the adhesive strength (N/mm 2) was measured. The measurement was performed 3 times, and the average value was obtained.
< Evaluation of thermosetting Property >)
Holes having a diameter of 5mm are formed in a 30mm×50mm×2mm thick silicone rubber sheet (AS wire) and a curable composition is embedded therein in an amount of 1 to 3mg, and heat curing is performed under the following conditions. The thermosetting properties were evaluated by the finger contact test of the cured product on the following basis.
< Curing Condition >
(1) Photo-curing
The curable composition was irradiated with ultraviolet light (peak wavelength: 365 nm) having an illuminance of 2500mW/cm 2 from two directions at an angle of 45℃using a UV-LED irradiation device UJ35 manufactured by Songshi Co., ltd. (the incident angle of light to the surface of a capacitor chip was 45 ℃), for 1.0 seconds (exposure 2500mJ/cm 2).
(2) Light and heat curing
The curable composition was irradiated with ultraviolet light (peak wavelength: 365 nm) having an illuminance of 2500mW/cm 2 from two directions at an angle of 45 ° (the incident angle of light to the surface of the capacitor chip was 45 °) for 1.0 seconds (exposure amount 2500mJ/cm 2) using a UV-LED irradiation device UJ35 manufactured by Songshi Co., ltd. Next, the irradiated curable composition was heated at 100℃for 30 minutes using a heated air circulation oven.
(3) Thermal curing
The curable composition was heated at 100℃for 30 minutes using a heated air circulation oven.
< Evaluation criterion >
(1) Evaluation criterion of adhesive Strength 1 after photo-curing
And (3) the following materials: 10N/mm 2 or more
O: 5N/mm 2 or more and less than 10N/mm 2
X: less than 5N/mm 2.
(2) Evaluation criterion of adhesive strength 2 after photo-curing
And (3) the following materials: 30N/mm 2 or more
O: 15N/mm 2 or more and less than 30N/mm 2
X: less than 15N/mm 2.
(3) Evaluation criterion of adhesive strength 3 after thermosetting
And (3) the following materials: 30N/mm 2 or more
O: 15N/mm 2 or more and less than 30N/mm 2
X: less than 15N/mm 2.
(4) Evaluation criterion for thermosetting property
And (3) the following materials: no change in the appearance of the cured product was observed even after the contact with the finger;
And (2) the following steps: after the finger is contacted, trace is slightly remained on the appearance of the cured product;
X: significant wrinkles were confirmed in the cured product.
3. Examples and comparative examples
Curable compositions of examples 1 to 14 and comparative examples 1 to 7 were prepared by blending the components in the amounts shown in the upper column of the following table. The "parts" described in the table represent "parts by weight" and "%" represents "% by weight". In the following table, "the molar ratio of the total of the acryl groups and the methacryl groups in the component (1) and the epoxy groups in the component (2) to the mercapto groups in the component (3)" is described in the column "((meth) acryl+epoxy group)/mercapto group", and "the amount of the component (3) relative to the entire curable composition" is described in the column "the amount of the component (3)".
In examples 1 to 13 and comparative example 7, components (1) and (2) were mixed and dissolved at 100℃and then cooled sufficiently to room temperature (20 to 25 ℃) and then component (5) was added thereto to disperse it sufficiently, and components (3) and (4) were added thereto to mix them and then left to stand for deaeration to prepare a curable composition. The preparation operation other than the mixing and dissolution of the components (1) and (2) was performed at room temperature.
In example 14, components (1) and (2) were mixed and dissolved at 100 ℃, and after cooling to room temperature (20 to 25 ℃) sufficiently, component (5) was added thereto to disperse it sufficiently, components (3) and (4) were added thereto and mixed, and component (6) was added thereto, and after mixing, the mixture was allowed to stand and defoamed to prepare a curable composition. The preparation operation other than the mixing and dissolution of the components (1) and (2) was performed at room temperature.
In comparative example 1, component (5) was added to component (1) and dispersed sufficiently, components (3) and (4) were added thereto, and after mixing, the mixture was left to stand for deaeration to prepare a curable composition. The preparation operation was performed at room temperature.
In comparative examples 2 to 5, the curable composition was prepared by mixing the components (1) and (2'), adding the component (5) thereto, dispersing the mixture sufficiently, adding the components (3) and (4) thereto, mixing the mixture, and then standing the mixture for deaeration. The preparation operation was performed at room temperature.
In comparative example 6, components (1) and (2) were mixed and dissolved at 100℃and cooled sufficiently to room temperature (20 to 25 ℃) and then component (5) was added thereto to disperse it sufficiently, and component (4) was added thereto to mix and then left to stand for deaeration to prepare a curable composition. The preparation operation other than the mixing and dissolution of the components (1) and (2) was performed at room temperature.
The results of evaluation tests of the curable compositions of examples 1 to 14 and comparative examples 1 to 7 are shown in the following table.
TABLE 1
。
TABLE 2
。
TABLE 3
。
From the results of examples 1 to 14, it is evident that the curable composition of the present invention has both excellent thermosetting properties and excellent photo-curability. Therefore, depending on the use environment and the application, the curing by heating and the curing by light irradiation may be selected and performed, or the two may be performed in combination. The cured product obtained by curing has high adhesive strength per unit area, and is useful as an adhesive for bonding between constituent members in a camera module. In contrast, the curable compositions of comparative examples 1 to 7 were insufficient in either thermosetting property or photocurability. In particular, the curable composition of comparative example 6 containing no component (3) and the curable composition of comparative example 7 containing a small amount of component (3) were insufficient in thermosetting property.
Industrial applicability
The curable composition of the present invention can be used for adhesives, sealants, coating agents (particularly adhesives for manufacturing camera modules), and the like.

Claims (11)

1. A curable composition comprising the following components (1) to (5):
(1) A compound having a (meth) acryloyl group,
(2) An epoxy compound having 2 or more epoxy groups in 1 molecule and being solid at 25℃,
(3) A polythiol compound having 2 or more mercapto groups in 1 molecule,
(4) Photoradical generator
(5) A latent curing agent, which is a curing agent,
The amount of the component (3) is 15 to 50 wt% based on the entire curable composition, and the molar ratio of the total of the acryl, methacryl and epoxy groups in the component (1) to the mercapto groups in the component (3), that is, the total of the acryl, methacryl and epoxy groups in the component (1) per the mercapto groups in the component (3), is 0.5 to 2.0.
2. The curable composition according to claim 1, wherein component (2) comprises at least one selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, dicyclopentadiene type epoxy resins, and biphenyl type epoxy resins.
3. The curable composition according to claim 1 or 2, wherein component (3) comprises a polythiol compound having 2 to 6 mercapto groups in 1 molecule.
4. The curable composition according to claim 1 or 2, wherein the amount of the component (3) is 25% by weight or more and 45% by weight or less relative to the entire curable composition.
5. The curable composition according to claim 1 or 2, wherein the molar ratio of the total of the acryl, methacryl groups in component (1) and the epoxy groups in component (2) to the mercapto groups in component (3), i.e., the total of the acryl, methacryl groups in component (1) and the epoxy groups in component (2), per the mercapto groups in component (3), is 0.7 to 1.5.
6. The curable composition according to claim 1 or 2, wherein component (5) comprises an amine-epoxy adduct-based compound and/or an amine-isocyanate adduct-based compound.
7. An adhesive comprising the curable composition according to any one of claims 1 to 6.
8. The adhesive according to claim 7, which is used for adhesion between constituent members of a camera module.
9. A sealant comprising the curable composition according to any one of claims 1 to 6.
10. A coating agent comprising the curable composition according to any one of claims 1 to 6.
11. A method for manufacturing a camera module, comprising the following steps (I) to (III):
(I) A step of positioning a first adhesive member and a second adhesive member coated with the curable composition according to any one of claims 1 to 6;
(II) a step of temporarily fixing the first adhesive member and the second adhesive member by curing the curable composition by irradiation with light; and
(III) a step of curing the curable composition by heating, thereby permanently fixing the first adhesive member and the second adhesive member.
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