CN112745793A - Curable composition - Google Patents

Curable composition Download PDF

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Publication number
CN112745793A
CN112745793A CN202011189242.1A CN202011189242A CN112745793A CN 112745793 A CN112745793 A CN 112745793A CN 202011189242 A CN202011189242 A CN 202011189242A CN 112745793 A CN112745793 A CN 112745793A
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China
Prior art keywords
meth
curable composition
compound
component
acrylate
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CN202011189242.1A
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Chinese (zh)
Inventor
田村贤
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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Priority claimed from JP2020170734A external-priority patent/JP2021075699A/en
Application filed by Ajinomoto Co Inc filed Critical Ajinomoto Co Inc
Publication of CN112745793A publication Critical patent/CN112745793A/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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • 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
    • 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
    • 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
    • H04N23/54—Mounting of pick-up tubes, electronic image sensors, deviation or focusing coils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Multimedia (AREA)
  • Signal Processing (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention addresses the problem of providing a curable composition that has both excellent photocurability and excellent thermosetting properties, has a low viscosity, and has a small cure shrinkage. The solution of the present invention is a curable composition comprising the following components (1) to (4): (1) a compound having a (meth) acryloyl group, (2) a polythiol compound having 2 or more mercapto groups in 1 molecule, (3) a photoradical generator, and (4) a latent curing agent, wherein the component (1) comprises a component (1-1): (1-1) a compound having a poly (oxyalkylene) chain and a (meth) acryloyl equivalent weight of 300 or more.

Description

Curable composition
Technical Field
The present invention relates to a curable composition.
Background
In recent years, with the development of higher functions of portable devices such as smartphones, camera modules (camera modules) mounted on portable devices such as smartphones have been increased in pixel size. Further, due to miniaturization and high functionality of the camera module, positional accuracy of, for example, a lens and an image sensor becomes very important.
On the other hand, in order to avoid thermal damage caused by high-temperature processing on an image sensor or the like, an adhesive used for the assembly of a camera module is required to have low-temperature curability, and in addition, 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 at the same time. From such a viewpoint, ultraviolet-curable adhesives and thermosetting epoxy resin adhesives are often used as adhesives that are curable at low temperatures and in a short time (for example, patent documents 1 and 2). However, the other side of the ultraviolet curable adhesive which can be cured quickly has large shrinkage during curing, and positional deviation (misalignment) of the member occurs after curing. On the other hand, the thermosetting epoxy resin adhesive is not necessarily satisfactory because it is a low-temperature and short-time curable adhesive, but it is necessary to fix the components to be bonded with a jig or a device in order to maintain the bonding posture during the bonding, and the viscosity may decrease due to the temperature increase caused by heating, which may cause the positional displacement of the components.
In order to solve the above-described problems, there have been proposed several types of adhesives that temporarily fix the components constituting the camera module by curing (precuring) by light (ultraviolet rays or visible light) irradiation and bond (main fix) the components by curing (main curing) by heat in order to accurately arrange the components (for example, patent documents 3 and 4).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2004-140497
Patent document 2: japanese laid-open patent publication No. 2013-88525
Patent document 3: japanese laid-open patent publication No. 2009-51954
Patent document 4: japanese patent laid-open No. 2009-79216.
Disclosure of Invention
Problems to be solved by the invention
Even when an adhesive that is light and thermosetting such as those described in patent documents 3 and 4 is used, there is a problem that a positional shift of a component due to shrinkage occurs when the curing shrinkage rate of the adhesive is large. Further, when the viscosity of the adhesive is high, the workability of the adhesive (ease of application, etc.) is lowered.
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 (thermosetting), and having a low viscosity and a small cure shrinkage ratio.
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 (4),
(1) a compound having a (meth) acryloyl group,
(2) A polythiol compound having 2 or more mercapto groups in 1 molecule,
(3) Photo radical generating agent, and
(4) a latent curing agent which is capable of curing,
wherein the component (1) comprises the following components (1-1):
(1-1) a compound having a poly (oxyalkylene) chain and a (meth) acryloyl group, and having a (meth) acryloyl equivalent weight of 300 or more;
[2] the curable composition according to the above [1], wherein the poly (oxyalkylene) chain comprises at least one member selected from the group consisting of an oxyethylene unit, an oxypropylene unit and an oxybutylene unit;
[3] the curable composition according to the above [1] or [2], wherein the amount of the component (1-1) is 15 to 100 parts by weight per 100 parts by weight of the component (1);
[4] the curable composition according to any one of the above [1] to [3], wherein the component (2) comprises a polythiol compound having 2 to 6 mercapto groups in 1 molecule;
[5] the curable composition according to any one of the above [1] to [4], wherein the molar ratio of the total of acryloyl groups and methacryloyl groups in the component (1) to mercapto groups in the component (2) (total of acryloyl groups and methacryloyl groups in the component (1)/mercapto groups in the component (2)) is 0.5 to 2.0;
[6] the curable composition according to any one of the above [1] to [5], wherein the component (4) comprises an amine-epoxy adduct compound and/or an amine-isocyanate adduct compound;
[7] an adhesive comprising the curable composition according to any one of the above [1] to [6 ];
[8] the adhesive according to the above [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 the above [1] to [6 ];
[10] a coating agent comprising the curable composition according to any one of the above [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 the above [1] to [6 ];
(II) curing the curable composition by light irradiation to temporarily fix the first adhesive member and the second adhesive member; and
(III) curing the curable composition by heating to permanently fix the first adhesive member and the second adhesive member.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a curable composition having both excellent photocurability and excellent thermosetting property, a low viscosity, and a small cure shrinkage can be obtained.
Detailed Description
< curable composition >
The curable composition of the present invention comprises the following components (1) to (4):
(1) a compound having a (meth) acryloyl group,
(2) A polythiol compound having 2 or more mercapto groups in 1 molecule (hereinafter, sometimes simply referred to as "polythiol compound"), (ii) a polythiol compound having a thiol group in 1 molecule, and a method for producing the same,
(3) Photo radical generating agent, and
(4) a latent curing agent.
One of the features of the present invention is that the component (1) contains the following components (1-1):
(1-1) a compound having a poly (oxyalkylene) chain and a (meth) acryloyl group, and having a (meth) acryloyl equivalent weight of 300 or more. By using the component (1-1), a curable composition having both excellent photocurability and excellent thermosetting property and a small cure shrinkage can be obtained.
The curable composition of the present invention has a feature of low viscosity. From the viewpoint of handling properties, the viscosity of the curable composition of the present invention is preferably less than 10Pa seeds, more preferably less than 8Pa seeds. The lower limit of the viscosity of the curable composition of the present invention is not particularly limited, and the viscosity is preferably 0.05Pa, more preferably 0.1Pa, or more. The viscosity of the curable composition is measured at a temperature: 25 ℃ and rotation speed: 20rpm and rotor: values measured using an E-type viscometer under the condition of 3 ° × R9.7.
The components (1) to (4) and the component (1-1) may be used alone in 1 kind, or 2 or more kinds may be used in combination. When the curable composition of the present invention contains components (1) to (4) and components other than component (1-1), only 1 kind of the components may be used, or 2 or more kinds may be used in combination. The respective components will be explained in turn below.
< (1) Compound having a (meth) acryloyl group
In the present invention, the compound having a (meth) acryloyl group used as the component (1) mainly acts to improve the adhesive strength. In the present invention, "(meth) acryloyl group" means either or both of an acryloyl group and a methacryloyl group.
The component (1) contains a compound having a poly (oxyalkylene) chain and a (meth) acryloyl equivalent weight of 300 or more (hereinafter, may be referred to simply as the component (1-1) of the "POA- (meth) acryloyl compound"). In the present invention, "poly (oxyalkylene) chain" refers to the formula: - (O-R)n(wherein R represents an alkylene group, and n represents a number of 2 or more.) has a chemical structure. The alkylene group in the poly (oxyalkylene) chain may be linear or branched. In addition, the formula: the number of oxyalkylene units represented by- (O-R) -i.e., n, may be a fractional number. In addition, a compound having only an oxyalkylene unit in which n is 1 and having no poly (oxyalkylene) chain (for example, ethylene glycol di (meth) acrylate) is not included in the POA- (meth) acryloyl compound.
The (meth) acryloyl equivalent weight of the POA- (meth) acryloyl compound refers to a value obtained by dividing the weight average molecular weight of the compound by the number of (meth) acryloyl groups in 1 molecule of the compound ((meth) acryloyl equivalent weight being the weight average molecular weight per the number of (meth) acryloyl groups in 1 molecule).
The POA- (meth) acryloyl compound has a poly (oxyalkylene) chain composed of oxyalkylene units, and therefore, a weight average molecular weight is used as a molecular weight for calculating the (meth) acryloyl equivalent thereof. The weight average molecular weight can be measured by a Gel Permeation Chromatography (GPC) method. Specifically, the weight average molecular weight can be calculated as follows: the measurement was carried out at a column temperature of 40 ℃ using LC-9A/RID-6A manufactured by Shimadzu corporation as a measuring apparatus, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko K.K. as a column, chloroform or the like as a mobile phase, and the calculation was carried out using a standard curve of standard polystyrene.
From the viewpoint of curability, viscosity and cure shrinkage of the curable composition, the weight average molecular weight of the POA- (meth) acryloyl compound is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, preferably 4000 or less, more preferably 3000 or less, still more preferably 2000 or less.
When the POA- (meth) acryloyl compound is a mixture, the number of (meth) acryloyl groups in 1 molecule of the compound represents an average value per 1 molecule. In addition, when both acryloyl and methacryloyl groups are present in 1 molecule of the compound, the number refers to the total number of acryloyl and methacryloyl groups in 1 molecule.
The number of (meth) acryloyl groups in 1 molecule of the POA- (meth) acryloyl compound can be calculated, for example, from the weight average molecular weight and the iodine value measured by the method specified in JIS K0070.
The number of (meth) acryloyl groups in 1 molecule of the POA- (meth) acryloyl compound is preferably 1 to 6, more preferably 2 to 5, and even more preferably 2 to 4, from the viewpoint of curability, viscosity, and cure shrinkage of the curable composition.
The (meth) acryloyl equivalent weight of the POA- (meth) acryloyl compound needs to be 300 or more. From the viewpoint of curability, viscosity and cure shrinkage of the curable composition, the equivalent weight of the (meth) acryloyl group is preferably 320 or more, more preferably 350 or more. On the other hand, the equivalent weight of the (meth) acryloyl group is preferably 1000 or less, more preferably 800 or less, from the viewpoint of curability and viscosity.
The poly (oxyalkylene) chain of the POA- (meth) acryloyl compound preferably contains at least one member selected from the group consisting of oxyethylene units, oxypropylene units and oxybutylene units, and more preferably comprises at least one member selected from the group consisting of oxyethylene units, oxypropylene units and oxybutylene units. Here, the oxypropylene unit may be linear (i.e., -O- (CH)2)3-, may also be branched (e.g. -O-CH)2-CH(CH3) -). Alternatively, the oxybutylene unit may be linear (i.e., -O- (CH)2)4-, may also be branched (e.g. -O-CH)2-CH(CH2CH3)-)。
Examples of the POA- (meth) acryloyl compound include the following compounds. In the following compounds, only 1 species may be used, or 2 or more species may be used in combination.
(POA- (meth) acryloyl compound having 1 acryloyl group or methacryloyl group in 1 molecule)
Methoxypolyethylene glycol (meth) acrylate
Methoxypolypropylene glycol (meth) acrylate
Methoxy polytetramethylene glycol (meth) acrylate
Phenoxy polyethylene glycol (meth) acrylates
Nonylphenoxy polyethylene glycol (meth) acrylate
In the present invention, "(meth) acrylate" means either or both of acrylate and methacrylate.
(POA- (meth) acryloyl compound having 2 (meth) acryloyl groups in 1 molecule)
Polyethylene glycol di (meth) acrylate
Polypropylene glycol di (meth) acrylate
Polytetramethylene glycol di (meth) acrylate
EO-modified bisphenol A di (meth) acrylate
PO-modified bisphenol A di (meth) acrylate
EO-modified bisphenol F di (meth) acrylate
PO-modified bisphenol F di (meth) acrylate
In the present invention, "EO modification" means modification by addition of Ethylene Oxide (EO). The term "PO modification" refers to modification by addition of Propylene Oxide (PO).
(Compound having 3 or more (meth) acryloyl groups in 1 molecule)
Ethoxylated pentaerythritol tetra (meth) acrylate
Here, the ethoxylated pentaerythritol tetra (meth) acrylate refers to a compound having a structure in which "pentaerythritol having a poly (oxyethylene) chain" and "4 (meth) acrylates" are bonded via an ester bond.
The component (1-1) preferably contains at least one selected from the group consisting of polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate, more preferably at least one selected from the group consisting of polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate.
The amount of the component (1-1) is preferably 15 to 100 parts by weight, more preferably 19.5 to 100 parts by weight, further preferably 19.5 to 99.5 parts by weight, per 100 parts by weight of the component (1), from the viewpoint of curability, viscosity and cure shrinkage of the curable composition.
Next, a compound having a (meth) acryloyl group other than the POA- (meth) acryloyl compound (hereinafter, may be simply referred to as a "(meth) acryloyl compound") will be described. The number of (meth) acryloyl groups in 1 molecule of the (meth) acryloyl compound may be 1 or more. When the (meth) acryloyl compound is a mixture, the number represents an average value per 1 molecule. In addition, when both acryloyl and methacryloyl groups are present in 1 molecule, the number refers to the total number of acryloyl and methacryloyl groups in 1 molecule. The number of (meth) acryloyl groups in 1 molecule of the (meth) acryloyl compound (excluding the phosphoric acid-modified (meth) acrylate described later) is preferably 1 to 6, more preferably 2 to 6, and still more preferably 2 to 4.
The molecular weight of the (meth) acryloyl compound (excluding the phosphoric acid-modified (meth) acrylate described later) is preferably 50 to 5000, more preferably 70 to 4000, and still more preferably 100 to 2000. When the molecular weight is less than 50, the volatility is high, and the composition is not good in terms of odor and handling property, and when the molecular weight exceeds 5000, the viscosity of the composition becomes high, and the coatability of the composition tends to be lowered. The molecular weight of 1000 or more means a weight average molecular weight, and can be measured by Gel Permeation Chromatography (GPC). Molecular weights of less than 1000 can be determined using a gravimetric device (e.g., ESI-MS).
Examples of the (meth) acryloyl compound include the following compounds. In the following compounds, only 1 species may be used, or 2 or more species may be used in combination.
(meth) acryloyl Compound having 1 acryloyl or methacryloyl group in 1 molecule)
Beta-carboxyethyl (meth) acrylate
Isobornyl (meth) acrylate
Octyl/decyl (meth) acrylate
Ethoxylated phenyl (meth) acrylate
N- (meth) acryloyloxyethyl hexahydrophthalimide
Omega-carboxy-polycaprolactone mono (meth) acrylates
Phthalic acid monohydroxyethyl (meth) acrylate
2-hydroxy-3-phenoxypropyl (meth) acrylate.
(meth) acryloyl Compound having 2 (meth) acryloyl groups in 1 molecule)
1, 6-hexanediol di (meth) acrylate
Ethylene glycol di (meth) acrylate
Propylene glycol di (meth) acrylate
Tetramethylene glycol di (meth) acrylate
Dicyclodecane dimethanol di (meth) acrylate
Neopentyl glycol hydroxypivalate di (meth) acrylate
Polyurethane having 2 (meth) acryloyl groups in 1 molecule
Polyester having 2 (meth) acryloyl groups in 1 molecule
Bisphenol A type epoxy (meth) acrylate
Caprolactone-modified epoxy (meth) acrylates
Here, caprolactone-modified epoxy (meth) acrylate having 2 (meth) acryloyl groups in 1 molecule (in the present specification, may be simply referred to as "caprolactone-modified epoxy (meth) acrylate") refers to a compound which can be produced by reacting epsilon-caprolactone with (meth) acrylic acid to produce a carboxylic acid compound, and then reacting the carboxylic acid compound with a difunctional epoxy compound.
(meth) acryloyl Compound having 3 or more (meth) acryloyl groups in 1 molecule)
Trimethylolpropane tri (meth) acrylate
Pentaerythritol (tri/tetra) (meth) acrylate
Glycerol propoxytris (meth) acrylate
Di (trimethylolpropane) tetra (meth) acrylate
Dipentaerythritol (penta/hexa) (meth) acrylate
Dipentaerythritol hexa (meth) acrylate
Polyurethane having 3 or more (meth) acryloyl groups in 1 molecule
A polyester having 3 or more (meth) acryloyl groups in 1 molecule.
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, in terms of weight ratio.
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, more preferably 30/70 to 70/30, in terms of weight ratio.
Among the above (meth) acryloyl compounds, tricyclodecane dimethanol di (meth) acrylate, bisphenol A type epoxy (meth) acrylate, caprolactone-modified epoxy (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are preferred, and bisphenol A type epoxy (meth) acrylate is more preferred.
From the viewpoint of storage stability, 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 only 1 kind, or 2 or more kinds may be used in combination. 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 these methods;
(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 aforementioned method (i), can be produced, for example, by the following methods (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 (e.g., alkylene glycol, glycerin, etc.) in such a ratio that the hydroxyl group of the polyol remains;
(iii) a method of adding an alkylene oxide (e.g., ethylene oxide, propylene oxide, etc.) to (meth) acrylic acid.
The phosphoric acid-modified (meth) acrylate may be a commercially available one. Examples of the commercially available products include "EBECRYL 168" manufactured by ALLNEX K.K., "KAYAMER PM-2" and "KAYAMER PM-21" manufactured by Nippon Kagaku K.K., "LIGHT ESTER P-1M", "LIGHT ESTER P-2M", "LIGHT ACRYLATE P-1A (N)", and "JPA-514" manufactured by North City chemical industry K.K.
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, and 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, and further 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, and still more preferably 0.05 to 2 parts by weight, per 100 parts by weight of the component (1), from the viewpoint of storage stability.
From the viewpoint of curability of the curable composition, the component (1) is preferably a compound containing 2 or more (meth) acryloyl groups in 1 molecule. The compound having 2 or more (meth) acryloyl groups in 1 molecule may be the POA- (meth) acryloyl compound or a compound other than the POA- (meth) acryloyl compound (i.e., the (meth) acryloyl compound). When a compound having 2 or more (meth) acryloyl groups in 1 molecule is used, the amount thereof is preferably 10 to 100 parts by weight, more preferably 20 to 100 parts by weight, and still more preferably 30 to 99.5 parts by weight, per 100 parts by weight of the component (1), from the viewpoint of curability of the curable composition.
In one embodiment of the present invention, the component (1) preferably comprises the component (1-1) and a phosphoric acid-modified (meth) acrylate, more preferably a mixture of the component (1-1) and a phosphoric acid-modified (meth) acrylate. In this embodiment, the component (1-1) preferably contains at least one selected from the group consisting of polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate, more preferably at least one selected from the group consisting of polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate.
In another embodiment of the present invention, the component (1) preferably contains at least one selected from the group consisting of tricyclodecane dimethanol di (meth) acrylate, bisphenol a type epoxy (meth) acrylate, caprolactone-modified epoxy (meth) acrylate and dipentaerythritol hexa (meth) acrylate, the component (1-1), and phosphoric acid-modified (meth) acrylate, and more preferably a mixture of at least one selected from the group consisting of tricyclodecane dimethanol di (meth) acrylate, bisphenol a type epoxy (meth) acrylate, caprolactone-modified epoxy (meth) acrylate and dipentaerythritol hexa (meth) acrylate, the component (1-1), and phosphoric acid-modified (meth) acrylate. In this embodiment, the component (1-1) preferably contains at least one selected from the group consisting of polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate, more preferably at least one selected from the group consisting of polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate.
In another embodiment of the present invention, the component (1) is preferably a mixture containing the component (1-1), bisphenol a type epoxy (meth) acrylate, and phosphoric acid-modified (meth) acrylate, more preferably the component (1-1), bisphenol a type epoxy (meth) acrylate, and phosphoric acid-modified (meth) acrylate. In this embodiment, the component (1-1) preferably contains at least one selected from the group consisting of polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate, more preferably at least one selected from the group consisting of polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate.
The amount of the component (1) is preferably 10% by weight or more, more preferably 15% by weight or more, further preferably 20% by weight or more, preferably 80% by weight or less, more preferably 75% by weight or less, further more preferably 70% by weight or less based on the whole curable composition, from the viewpoint of curability, viscosity and cure shrinkage of the curable composition.
< (2) polythiol compound
In the present invention, the "polythiol compound having 2 or more mercapto groups in 1 molecule" used as the component (2) mainly functions as a curing agent which reacts with the component (1) by irradiation with light such as ultraviolet rays and cures the composition. The number of mercapto groups in 1 molecule of the polythiol compound is preferably 2 to 6, more preferably 3 to 6, further preferably 3 to 5, particularly preferably 3 or 4.
The polythiol compound may be a commercially available compound, or a compound produced by a known method (for example, the method described in Japanese patent laid-open No. 2012-153794 or International publication No. 2001/00698) may be used.
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 is an ester of a polyhydric alcohol and a carboxylic acid, and is an ester in which a part of hydroxyl groups of the polyhydric alcohol forms an ester bond; full esters are esters in which all of the 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 mercaptoorganic acid include mercaptoaliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid (e.g., 3-mercaptopropionic acid), and mercaptobutyric acid (e.g., 3-mercaptobutyric acid and 4-mercaptobutyric acid); esters containing a mercapto group and a carboxyl group obtained by esterification of a hydroxy acid with a mercapto organic acid; mercapto aliphatic dicarboxylic acids such as mercaptosuccinic acid and dimercaptosuccinic acid (e.g., 2, 3-dimercaptosuccinic acid); mercapto aromatic monocarboxylic acids such as mercaptobenzoic acid (e.g., 4-mercaptobenzoic acid); and so on. The mercapto aliphatic monocarboxylic acid preferably has 2 to 8, more preferably 2 to 6, further preferably 2 to 4, particularly preferably 3 carbon atoms. Among the above mercapto organic acids, preferred are mercapto aliphatic monocarboxylic acids having 2 to 8 carbon atoms, more preferred are mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid and 4-mercaptobutyric acid, and still more preferred is 3-mercaptopropionic acid.
Specific examples of partial esters of a polyhydric alcohol and a mercapto organic acid include: trimethylolethane bis (mercaptoacetic acid) ester, trimethylolethane bis (3-mercaptopropionic acid) ester, trimethylolethane bis (3-mercaptobutanoic acid) ester, trimethylolethane bis (4-mercaptobutanoic acid) ester, trimethylolpropane bis (mercaptoacetic acid) ester, trimethylolpropane bis (3-mercaptopropionic acid) ester, trimethylolpropane bis (3-mercaptobutanoic acid) ester, trimethylolpropane bis (4-mercaptobutanoic acid) ester, pentaerythritol tris (mercaptoacetic acid) ester, pentaerythritol tris (3-mercaptopropionic acid) ester, pentaerythritol tris (3-mercaptobutanoic acid) ester, pentaerythritol tris (4-mercaptobutanoic acid) ester, dipentaerythritol tetrakis (mercaptoacetic acid) ester, dipentaerythritol tetrakis (3-mercaptopropionic acid) ester, dipentaerythritol tetrakis (3-mercaptobutanoic acid) ester, Dipentaerythritol tetrakis (4-mercaptobutanoic acid) ester, 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 (3-mercaptobutyrate), trimethylolethane tris (4-mercaptobutyrate), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (4-mercaptobutyrate), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (4-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate), ethylene glycol bis (4-mercaptobutyrate), trimethylolpropane tris (3-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (4-mercaptobutyrate), pentaerythritol tetrakis (4-mercaptobutyrate), and mixtures thereof, Dipentaerythritol hexa (mercaptoacetic) ester, dipentaerythritol hexa (3-mercaptopropionic) ester, dipentaerythritol hexa (3-mercaptobutanoic) ester, dipentaerythritol hexa (4-mercaptobutanoic) ester, and the like.
From the viewpoint of storage stability, the partial ester and the full ester are preferably those having a very small amount of basic impurities, and more preferably those not requiring the use of a basic substance in production.
Further, as the component (2), alkane polythiol compounds such as 1, 4-butanedithiol, 1, 6-hexanedithiol, and 1, 10-decanedithiol; polyether containing a terminal mercapto group, etc.; terminal mercapto group-containing polythioethers and the like; polythiol compounds obtained by reacting an epoxy compound with hydrogen sulfide, and the like; a polythiol compound produced by using a basic substance as a reaction catalyst in the production process thereof, such as a polythiol compound having a terminal mercapto group obtained by a reaction between a polythiol compound and an epoxy compound. The polythiol compound produced by using a basic substance is preferably used after dealkalization treatment is carried out so that the concentration of basic metal (alkali metal) ions is 50 ppm by weight or less.
Examples of the dealkalization treatment of the polythiol compound produced using an alkaline substance include 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, followed by desalting by extraction, washing, or the like; a method of performing adsorption using an ion exchange resin; a method of purifying by distillation, and the like, but is not limited to these methods.
Further, as the component (2), for example, tris [ (3-mercaptopropionyloxy) ethyl ] isocyanurate, 1,3, 5-tris (3-mercaptobutyryloxyethyl) -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' -isopropylidenediphenylbis (3-mercaptopropyl) ether and the like can be used.
The component (2) preferably contains a polythiol compound having 2 to 6, more preferably 3 to 6, further more preferably 3 to 5, particularly preferably 3 or 4 mercapto groups in 1 molecule.
In one embodiment of the present invention, the component (2) preferably contains at least one selected from pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercaptopropyl) isocyanurate, more preferably at least one selected from pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercaptopropyl) isocyanurate.
In another embodiment of the present invention, component (2) preferably comprises pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), or tris (3-mercaptopropyl) isocyanurate, more preferably pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), or tris (3-mercaptopropyl) isocyanurate, and still more preferably pentaerythritol tetrakis (3-mercaptopropionate).
From the viewpoint of curability, the molar ratio of the total of acryloyl groups and methacryloyl groups in the component (1) to mercapto groups in the component (2) (total of acryloyl groups and methacryloyl groups in the component (1)/mercapto groups in the component (2)) is preferably 0.5 to 2.0, more preferably 0.6 to 1.6, even more preferably 0.7 to 1.5, and particularly preferably 0.8 to 1.3.
The amount of the component (2) is preferably 10% by weight or more, more preferably 15% by weight or more, further preferably 20% by weight or more, preferably 50% by weight or less, more preferably 45% by weight or less, further more preferably 40% by weight or less based on the whole curable composition, from the viewpoint of curability, viscosity and cure shrinkage of the curable composition.
< (3) photo radical generator
In the present invention, the photo radical generator used as the component (3) is not particularly limited. Examples of the photoradical generator include: phenylalkylketone (alkylphenone) type photo radical generators, acylphosphine oxide type photo radical generators, oxime ester type photo radical generators, α -hydroxyketone type photo radical generators, and the like. The photoradical generator is preferably a phenylalkylketone photoradical generator.
Examples of the phenylalkylketone photoradical generators include: 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] - [4- (4-morpholinyl) phenyl ] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2-diethoxyacetophenone, 2, 4-diethylthioxanthone, diphenyl- (2,4, 6-trimethylbenzoyl) phosphine oxide, ethyl (2,4, 6-trimethylbenzoyl) phenylphosphinate, 4' -bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenyl ketone, 2-dimethoxy-1, 2-diphenylethan-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, oligomers of 2-hydroxy-1- (4-isopropenylphenyl) -2-methylpropan-1-one, and the like.
Examples of the acylphosphine oxide photoradical generator include: 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and the like.
Examples of the oxime ester photoradical generators include: 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), 1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone O-acetyloxime, and the like.
Examples of the α -hydroxyketone photoradical 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 commercially available photoradical generators include: "Irgacure 1173" (2-hydroxy-2-methyl-1-phenylpropan-1-one), "Irgacure OXE 01" (1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), "Irgacure OXE 02" (1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone O-acetyloxime), manufactured by BASF corporation, "Esacure KTO 46" (a mixture of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 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), etc.
The amount of the component (3) is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, and still more preferably 0.1% by weight or more based on the whole curable composition, from the viewpoint of obtaining a curable composition which can be efficiently photocured upon light irradiation. On the other hand, the amount of the component (3) is preferably 10% by weight or less, more preferably 5% by weight or less, and further more preferably 2% by weight or less based on the whole curable composition, from the viewpoint of suppressing outgas (outgas) due to the photo radical generator or its decomposition product remaining in the cured product.
< (4) latent curing agent
In the present invention, the latent curing agent used as the component (4) is an additive known in the field of epoxy resins and the like, which does not cure the epoxy resin and the like at normal temperature (25 ℃) but can cure the epoxy resin and the like by heating. In the present invention, the latent curing agent functions to promote the reaction between the component (1) (the compound having a (meth) acryloyl group) and the component (2) (the polythiol compound having 2 or more mercapto groups in 1 molecule).
Examples of the latent curing agent include imidazole compounds which are solid at ordinary temperature, amine-epoxy adduct compounds (reaction products of amine compounds and epoxy compounds), and amine-isocyanate adduct compounds (reaction products of amine compounds and isocyanate compounds).
Examples of the imidazole compound which is solid at room 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, 2-phenylimidazole, 2-phenyl, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, N- (2-methylimidazolium-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 epichlorohydrin with polyhydric phenols such as bisphenol a, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether ester obtained by reacting hydroxy acid such as p-hydroxybenzoic acid and β -hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; glycidylamine compounds obtained by reacting epichlorohydrin with 4,4' -diaminodiphenylmethane, m-aminophenol, or the like; and polyfunctional epoxy compounds such as epoxidized phenol novolak resins, epoxidized cresol novolak resins, and epoxidized polyolefins, or monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate; and so on.
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 (also referred to as an isocyanate group) in 1 molecule and 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; arylamine compounds such as 4,4' -diaminodiphenylmethane and 2-methylaniline; nitrogen atom-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2, 4-dimethylimidazoline, piperidine, piperazine and the like; and so on.
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-phenylimidazole Oxazoline, 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, alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group such as N-dimethylaminobenzoic acid, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N-dimethylglycine hydrazide, N-dimethylpropanoic hydrazide, nicotinoyl hydrazide, and isonicotinyl hydrazide (isoniazid); and so on.
When an amine-epoxy adduct-based compound is produced by addition reaction of an epoxy compound and an amine compound, 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, mercaptoacetic 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, p-phenylene diisocyanate, 1,3, 6-hexamethylene triisocyanate, bicycloheptane triisocyanate, etc.; and a compound containing a terminal isocyanate group obtained by reacting these polyfunctional isocyanate compounds with an active hydrogen compound; and so on. Examples of such a terminal isocyanate group-containing compound include: an adduct compound having a terminal isocyanate group obtained by a reaction of tolylene diisocyanate and trimethylolpropane, an adduct compound having a terminal isocyanate group obtained by a reaction of tolylene diisocyanate and pentaerythritol, and the like.
The latent curing agent can be easily obtained, for example, by: mixing the above raw materials, reacting at 20-200 deg.C, cooling, solidifying, and pulverizing; alternatively, the above-mentioned starting materials are reacted in a solvent such as methyl ethyl ketone, dioxane or tetrahydrofuran, and after removing the solvent, the solid content is pulverized.
Commercially available latent curing agents can be used. Examples of commercially available amine-epoxy adduct compounds include: "Ajicure PN-23", "Ajicure PN-40", "Ajicure PN-50", "Ajicure PN-H" manufactured by Ajinomoto Fine-technique Co., Ltd, "Harden X-3661S", "Harden X-3670S" manufactured by A.C. R. Co., Ltd, "NOVACURE HX-3742" and "NOVACURE HX-3721" manufactured by Asahi Kasei Co., Ltd. Further, commercially available products of the amine-isocyanate adduct-based compound include, for example: "Fujicure FXR-1000", "Fujicure FXR-1030", "Fujicure FXR-1020", "Fujicure FXR-1030", "Fujicure FXR-1081" and "Fujicure FXR-1121", manufactured by T & K TOKA, Ltd.
The component (4) preferably contains an amine-epoxy adduct compound and/or an amine-isocyanate adduct compound, more preferably an amine-epoxy adduct compound and/or an amine-isocyanate adduct compound, still more preferably an amine-epoxy adduct compound or an amine-isocyanate adduct compound, and particularly preferably an amine-epoxy adduct compound.
From the viewpoint of curability, the amount of the component (4) is preferably 1% by weight or more, more preferably 3% by weight or more, and still more preferably 5% by weight or more, based on the whole curable composition. From the viewpoint of storage stability, the amount of the component (4) 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 whole curable composition.
< (5) epoxy resin
The curable composition of the present invention may contain an epoxy resin as the component (5). Examples of the epoxy resin include: bisphenol A-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthol-type epoxy resin, naphthalene-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, bisphenol S-type epoxy resin, aromatic glycidyl amine-type epoxy resin (e.g., tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, bisphenol A novolac-type epoxy resin, epoxy resin having a butadiene structure, diglycidyl etherate of bisphenol, diglycidyl etherate of naphthalenediol, diglycidyl etherate of phenol, and diglycidyl etherate of alcohol, And alkyl substitutes, halides, hydrogenated products (hydrides) of these epoxy resins, and the like. The epoxy resin may be used in only 1 kind, or 2 or more kinds may be used in combination. The epoxy resin may be a liquid at 25 ℃ or a solid at 25 ℃. The epoxy resin may be a monomer (i.e., a monomeric epoxy resin).
From the viewpoint of temporary fixation and from the viewpoint of adhesion of a Liquid Crystal Polymer (LCP) or the like to a member which is difficult to adhere, the epoxy resin is more preferably an epoxy resin which has 2 or more epoxy groups in 1 molecule and is solid at 25 ℃. The epoxy resin may also contain a liquid epoxy resin that is liquid at 25 ℃, but from the viewpoint of the above-described effects, it is preferable that the epoxy resin does not contain a liquid epoxy resin, or contains a liquid epoxy resin in an amount of 20 parts by weight or less per 100 parts by weight of the epoxy resin. The amount of the liquid epoxy resin is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less, per 100 parts by weight of the epoxy resin. The epoxy resin particularly preferably does not contain a liquid epoxy resin.
From the viewpoint of reactivity and the like, the epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 100 to 3000, and further preferably 150 to 1000. Here, the epoxy equivalent means the number of grams (unit: g/eq) of the compound containing 1 gram equivalent of the epoxy group. In other words, the epoxy equivalent weight means a value obtained by dividing the molecular weight of a compound containing an epoxy group by the number of epoxy groups that the compound has, that is, the molecular weight per 1 epoxy group. The epoxy equivalent can be measured according to the method specified in JIS K7236.
In one embodiment of the present invention, the component (5) preferably contains at least one selected from the group consisting of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a dicyclopentadiene type epoxy resin, and a biphenyl type epoxy resin, and more preferably at least one selected from the group consisting of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a dicyclopentadiene type epoxy resin, and a biphenyl type epoxy resin. In this embodiment, the bisphenol a type epoxy resin, the bisphenol F type epoxy resin, the dicyclopentadiene type epoxy resin, and the 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 (5) preferably comprises 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, the bisphenol a type epoxy resin, the bisphenol F type epoxy resin, the dicyclopentadiene type epoxy resin, and the 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 (5) is preferably a bisphenol A type epoxy resin having 2 or more epoxy groups in 1 molecule and being solid at 25 ℃, more preferably a bisphenol A type epoxy resin having 2 or more epoxy groups in 1 molecule and being solid at 25 ℃.
When an epoxy resin is used as the component (5), the amount thereof is preferably 1% by weight or more, more preferably 3% by weight or more, further preferably 5% by weight or more, further preferably 70% by weight or less, further preferably 60% by weight or less, further preferably 55% by weight or less, based on the whole curable composition, from the viewpoint of curability.
< other ingredients >
The curable composition of the present invention may contain other components than the above components within a range not impairing the effects of the present invention. Examples of other components include: polymerization inhibitors (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 (alumina), zinc oxide, silica, potassium titanate, kaolin, talc, quartz powder, etc.); an organic filler containing a copolymer obtained by copolymerizing "polymethyl methacrylate and/or polystyrene" with "a monomer copolymerizable with these monomers"; a thixotropic agent; defoaming agents; leveling agent; a coupling agent; a flame retardant; a pigment; a dye; fluorescent agents, and the like. Only 1 type of the other components may be used, or 2 or more types may be used in combination.
< 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 respective components using a kneader, a stirring mixer, a three-roll mill, or the like, for example. The temperature of the curable composition during mixing is usually 10 to 50 ℃ and preferably 20 to 40 ℃.
The light to be irradiated when the curable composition of the present invention is photocured is preferably ultraviolet light. The peak wavelength of the irradiated light is preferably 300 to 500 nm. The illuminance of the irradiated light is preferably 100 to 5000mW/cm2More preferably 300 to 4000mW/cm2. The exposure is preferably 500 to 3000mJ/cm2More preferably 1000 to 3000mJ/cm2。
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 SPOT type UV irradiator, a xenon lamp, a DEEP UV lamp, and the like.
The heating temperature for heat curing the curable composition of the present invention is not particularly limited, and is, for example, 50 to 150 ℃ and preferably 60 to 100 ℃. 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 thus 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 components of the camera module.
Method for manufacturing camera module
The present invention provides a method for manufacturing a camera module, which includes 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 of the present invention;
(II) curing the curable composition by light irradiation to temporarily fix the first adhesive member and the second adhesive member; and
(III) curing the curable composition by heating to permanently fix the first adhesive member and the second adhesive member. Here, the first adhesive member refers to a member to which the curable composition of the present invention is applied, and the second adhesive member refers to another member to which the first adhesive member is adhered. 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 first adhesive member and the second adhesive member can be bonded to each other with high bonding strength while the respective members can be positioned with high accuracy, and as a result, a high-quality camera module can be efficiently manufactured.
In the step (II), there may be a case where an unirradiated portion where light is not irradiated to the applied curable composition remains due to the positional relationship between the first adhesive member and the second adhesive member. However, since the curable composition of the present invention has a good thermosetting property, the non-irradiated portion is sufficiently cured by the thermosetting in the step (III) to be finally cured, and a cured product having a high adhesive strength can be formed from the entire applied curable composition.
The conditions for light irradiation in step (II) and the conditions for heating in step (III) in the method for manufacturing a camera module according to the present invention are as described above.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples, and can be carried out by appropriately changing the examples within the scope capable of complying with the spirit described above/below, and all of them are included in the technical scope of the present invention.
1. Raw materials
< ingredient (1): compound having (meth) acryloyl group
(I) Component (1-1): a compound having a poly (oxyalkylene) chain and a (meth) acryloyl group and having a (meth) acryloyl equivalent weight of 300 or more
(1A) APG-700: manufactured by shinkamura chemical industries, polypropylene glycol # 700 diacrylate, weight average molecular weight: 808, 1 number of acryloyl groups in molecule: 2, (meth) acryloyl equivalent weight: 404
(1B) A-PTMG-65: polytetramethylene glycol 650 diacrylate, manufactured by shinkamura chemical industries, ltd.w.: 758, 1 number of acryloyl groups in molecule: 2, (meth) acryloyl equivalent weight: 379
(1C) ATM-35E: ethoxylated pentaerythritol tetraacrylate, manufactured by shinkamura chemical industries, having a weight average molecular weight: 1892, number of acryloyl groups in 1 molecule: 4, (meth) acryloyl equivalent weight: 473
(1D) A-1000: manufactured by shinkamura chemical industries, polyethylene glycol # 1000 diacrylate, weight average molecular weight: 1108, 1 number of acryloyl groups in molecule: 2, (meth) acryloyl equivalent weight: 554.
(II) component (1-1'): a compound having an oxyalkylene unit and a (meth) acryloyl group and having a (meth) acryloyl equivalent of less than 300
(1E) "M-313": a mixture of an isocyanuric acid EO-modified diacrylate and an isocyanuric acid EO-modified triacrylate (the content of the diacrylate compound: 35% by weight, the content of the triacrylate compound: 65% by weight), manufactured by Toyo Synthesis Ltd., weight average molecular weight: 404, 1 number of acryloyl groups in molecule: 2.65, (meth) acryloyl equivalent weight: 158.
(III) Compound having a (meth) acryloyl group other than component (1-1) and component (1-1')
(1F) EBECRYL 600: bisphenol A type epoxy acrylate manufactured by DAICEL-ALLNEX, molecular weight: 500, 1 number of acryloyl groups in molecule: 2
(1G) IRR-214K: dicidol diacrylate manufactured by DAICEL-ALLNEX, molecular weight: 300, 1 number of acryloyl groups in molecule: 2
(1H) DPHA: dipentaerythritol hexaacrylate manufactured by DAICEL-ALLNEX, molecular weight: 524, 1 number of acryloyl groups in molecule: 6
(1I) EBECRYL 3708: caprolactone-modified epoxy acrylate manufactured by DAICEL-ALLNEX, molecular weight: 1500, 1 number of acryloyl groups in molecule: 2
(1J) EBECRYL 168: phosphoric acid-modified methacrylate (manufactured by DAICEL-ALLNEX Co., Ltd., molecular weight: 270, 1 number of methacryloyl groups in molecule: 1.5.
< ingredient (2): polythiol compound
(2A) And (3) PEMP: pentaerythritol tetrakis (3-mercaptopropionate) manufactured by SC organic chemical corporation, molecular weight: 489, number of thiol groups in 1 molecule: 4
(2B) PE 1: karenz MT pentaerythritol tetrakis (3-mercaptobutanoic acid) ester manufactured by Showa Denko K.K., molecular weight: 544, number of thiol groups in 1 molecule: 4
(2C) TMPIC: tris (3-mercaptopropyl) isocyanurate, molecular weight: 351, 1 number of mercapto groups in molecule: 3.
< ingredient (3): photo radical generator
(3A) Irgacure 1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one manufactured by BASF
(3B) Escapure KIP 150: oligomer of 2-hydroxy-1- (4-isopropenylphenyl) -2-methylpropan-1-one manufactured by IGM Resins b.v.
< ingredient (4): latent curing agent
(4A) PN-23: amine-epoxy adduct-based Compound manufactured by Ajinomoto Fine Chemicals K.K
(4B) FXR 1081: amine-isocyanate adduct compound manufactured by K TOKA, Inc.
< ingredient (5): epoxy resin
(5A) jER 1001: bisphenol a epoxy resin manufactured by mitsubishi chemical corporation, epoxy Equivalent (EPW): 475g/eq, softening point: 64 ℃, number of epoxy groups in 1 molecule: 2
(5B) jER 4005P: bisphenol F type epoxy resin manufactured by mitsubishi chemical corporation, epoxy Equivalent (EPW): 538g/eq, softening point: 87 ℃, number of epoxy groups in 1 molecule: 2
(5C) HP-7200: dicyclopentadiene type epoxy resin manufactured by DIC corporation, epoxy Equivalent (EPW): 258g/eq, softening point: 56-66 ℃, number of epoxy groups in 1 molecule: 2 to 3
(5D) YX 4000H: biphenyl type epoxy resin manufactured by mitsubishi chemical corporation, epoxy Equivalent (EPW): 192g/eq, melting point: 105 ℃, number of epoxy groups in 1 molecule: 2.
2. evaluation test
< evaluation of viscosity >
At the temperature: 25 ℃ and rotation speed: 20rpm and rotor: the viscosity of the curable composition was measured using an E-type viscometer RE-80 manufactured by Toyobo industries, Ltd under a condition of 3 ℃ XR 9.7, and evaluated by the following criteria;
(evaluation criteria)
O: seeds with viscosity less than 10Pa
X: viscosity is 10Pa, more than seeds.
< evaluation of curability >
(1) Evaluation of Photocurability
A coating film of the curable composition was formed by spreading the curable composition to a thickness of about 50 μm on a glass epoxy resin laminate (FR-4.0, manufactured by Richang industries, Ltd.) having a width of 2.5mm × a length of 8.0mm × a thickness of 0.8mm by using a spacer and a glass rod having a thickness of about 50 μm, photocuring was performed under the following conditions, the appearance of the coating film after finger contact (appearance of the coating film due to finger contact) was observed, and photocuring was evaluated by the following criteria;
(curing conditions)
The UV-LED irradiation apparatus Unifield NF150 manufactured by USHIO Motor Co., Ltd was used to irradiate the coating film with an irradiation intensity of 10mW/cm2Ultraviolet (peak wavelength: 365nm) for 100 seconds (exposure amount 1000 mJ/cm)2)；
(evaluation criteria)
O: absence of uncured portions on the coating film
X: uncured portions are present on the coating film.
(2) Evaluation of photo-and thermosetting Properties
The coating film of the curable composition formed on the glass epoxy resin laminate in the same manner as described above was subjected to photo-and thermal-curing under the following conditions, the appearance of the coating film after finger contact was observed, and the photo-and thermal-curing properties were evaluated by the following criteria;
(curing conditions)
The UV-LED irradiation apparatus Unifield NF150 manufactured by USHIO Motor Co., Ltd was used to irradiate the coating film with an irradiation intensity of 10mW/cm2Ultraviolet (peak wavelength: 365nm) for 100 seconds (exposure amount 1000 mJ/cm)2) Subsequently, the light-irradiated coating film was heated at 100 ℃ for 30 minutes by means of a hot air circulating oven;
(evaluation criteria)
O: absence of uncured portions on the coating film
X: uncured portions are present on the coating film.
(3) Evaluation of thermosetting Properties
The coating film of the curable composition formed on the glass epoxy resin laminate in the same manner as described above was thermally cured under the following conditions, and the appearance of the coating film after contact with a finger was observed, and the thermosetting property was evaluated by the following criteria;
(curing conditions)
Heating the coating film at 100 ℃ for 30 minutes by utilizing a hot air circulating oven;
(evaluation criteria)
O: absence of uncured portions on the coating film
X: uncured portions are present on the coating film.
< evaluation of curing shrinkage >
The specific gravities of the curable composition before curing and a cured product thereof were measured by a dry automatic densitometer (AccuPyc (アキュピック) II1340) manufactured by shimadzu corporation, and the curing shrinkage was calculated by the following formula and evaluated according to the following criteria;
curing shrinkage (%) of { (specific gravity of cured product-specific gravity of curable composition before curing)/specific gravity of cured product } × 100
(evaluation criteria)
O: the curing shrinkage is less than 5%
X: the curing shrinkage is 5% or more.
The cured product was prepared as follows: the releasing surface of a released polyethylene terephthalate (PET) film (NS-80A) was coated with the curable composition, spread to a thickness of about 50 μm by a glass rod, and irradiated with 10mW/cm of UV-LED irradiation apparatus Unifield NF150 manufactured by USHIO Motor Co., Ltd2Ultraviolet (peak wavelength: 365nm) for 100 seconds (exposure amount 1000 mJ/cm)2) Subsequently, the light-irradiated curable composition was heated at 100 ℃ for 30 minutes by a hot air circulating oven.
3. Examples and comparative examples
The curable compositions of examples 1 to 15 and comparative examples 1 to 4 were prepared by mixing the respective components in the amounts shown in the upper column of the following table. In the table, "part" means "part by weight". In the following tables, the column of "(meth) acryloyl group/mercapto group" shows "the molar ratio of the total of acryloyl groups and methacryloyl groups in the component (1) to the mercapto group in the component (2)".
In examples 1 to 11 and comparative examples 1,2 and 4, the components (1) and (4) were sufficiently mixed, then the components (2) and (3) were added thereto, and mixed, followed by static defoaming to prepare a curable composition. In comparative example 3, the components (1) and (4) were sufficiently mixed, and then the component (3) was added thereto and mixed, followed by standing and defoaming to prepare a curable composition. In examples 12 to 15, the component (1) and the component (5) were mixed and dissolved at 100 ℃, sufficiently cooled to room temperature (20 to 25 ℃), then the component (4) was added thereto, mixed, the components (2) and (3) were added thereto, mixed, and then, allowed to stand for defoaming, thereby preparing a curable composition. The preparation operations in examples 1 to 15 and comparative examples 1 to 4 were carried out at room temperature, except for mixing and dissolving the component (1) and the component (5) in examples 12 to 15.
The results of the evaluation tests of the curable compositions of examples 1 to 15 and comparative examples 1 to 4 are shown in the following table.
[ Table 1]
Figure DEST_PATH_IMAGE001
。
[ Table 2]
Figure 411633DEST_PATH_IMAGE002
。
[ Table 3]
Figure DEST_PATH_IMAGE003
。
[ Table 4]
Figure 391090DEST_PATH_IMAGE004
。
From the results of examples 1 to 15, it is clear that the curable composition of the present invention has a low viscosity and is excellent in workability. Further, it is found that the curable composition of the present invention has a small cure shrinkage rate and can suppress the positional shift due to cure shrinkage. In contrast, the curable compositions of comparative examples 1 to 4 all had high cure shrinkage. Furthermore, the curable compositions of comparative examples 2 to 4 had high viscosity, and the curable composition of comparative example 3 had insufficient thermosetting property.
Industrial applicability of the invention
The curable composition of the present invention is useful for adhesives, sealants, coating agents (particularly, adhesives for use in the production of camera modules), and the like.

Claims (11)

1. A curable composition comprising the following components (1) to (4),
(1) a compound having a (meth) acryloyl group,
(2) A polythiol compound having 2 or more mercapto groups in 1 molecule,
(3) Photo radical generating agent, and
(4) a latent curing agent which is capable of curing,
wherein the component (1) comprises the following components (1-1):
(1-1) a compound having a poly (oxyalkylene) chain and a (meth) acryloyl group, and having a (meth) acryloyl equivalent weight of 300 or more.
2. The curable composition according to claim 1, wherein the poly (oxyalkylene) chain comprises at least one member selected from the group consisting of oxyethylene units, oxypropylene units and oxybutylene units.
3. The curable composition according to claim 1 or 2, wherein the amount of the component (1-1) is 15 to 100 parts by weight per 100 parts by weight of the component (1).
4. The curable composition according to claim 1 or 2, wherein the component (2) comprises a polythiol compound having 2 to 6 mercapto groups in 1 molecule.
5. The curable composition according to claim 1 or 2, wherein the molar ratio of the sum of acryloyl and methacryloyl groups in the component (1) to mercapto groups in the component (2) (sum of acryloyl and methacryloyl groups in the component (1)/mercapto groups in the component (2)) is 0.5 to 2.0.
6. The curable composition according to claim 1 or 2, wherein the component (4) comprises an amine-epoxy adduct compound and/or an amine-isocyanate adduct 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) curing the curable composition by light irradiation to temporarily fix the first adhesive member and the second adhesive member; and
(III) curing the curable composition by heating to permanently fix the first adhesive member and the second adhesive member.
CN202011189242.1A 2019-10-31 2020-10-30 Curable composition Pending CN112745793A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010254855A (en) * 2009-04-27 2010-11-11 Bridgestone Corp Adhesive composition
CN102786640A (en) * 2011-05-17 2012-11-21 日本化药株式会社 Energy ray curable resin composition for optical lens sheet, cured object thereof and optical lens sheet
CN107011514A (en) * 2015-11-30 2017-08-04 味之素株式会社 Light and heat hardening resin composition
WO2018181421A1 (en) * 2017-03-29 2018-10-04 味の素株式会社 Curable composition and structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010254855A (en) * 2009-04-27 2010-11-11 Bridgestone Corp Adhesive composition
CN102786640A (en) * 2011-05-17 2012-11-21 日本化药株式会社 Energy ray curable resin composition for optical lens sheet, cured object thereof and optical lens sheet
CN107011514A (en) * 2015-11-30 2017-08-04 味之素株式会社 Light and heat hardening resin composition
WO2018181421A1 (en) * 2017-03-29 2018-10-04 味の素株式会社 Curable composition and structure

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