JP4883264B2 - Heat-curing one-part resin composition - Google Patents

Description

  The present invention is a one-part resin composition that is excellent in rapid curability by heating at low temperature, has high adhesive strength, does not cause separation and uncuring during heat curing, and has good storage stability (storage stability). It is about.

  A compound having a thiirane ring in which all or part of oxygen atoms of the oxirane ring of the epoxy resin is replaced with a sulfur atom is known as an episulfide resin. Episulfide resins are known to have characteristics such as excellent low-temperature curability with amine compounds, good water resistance, high refractive index, and flame retardancy compared to epoxy resins. However, most of the conventional episulfide-based compositions are two-component type, requiring complicated steps such as weighing, mixing, and defoaming the resin component and the curing agent immediately before actual use. Since the usable period is limited and there is a possibility of mixing errors, the workability and reliability are inferior. For example, JP-A-50-124952, JP-A-11-140161, and JP-A-2002-173533 show episulfide resin-based compositions that are cured at a lower temperature than epoxy resin-based compositions. These compositions are two-component and have the above-mentioned problems in workability and reliability.

As a technique for solving this problem, the problem of the two-component composition as described above was solved by using a so-called latent curing agent that does not react with the episulfide resin at room temperature and exhibits reactivity by stimulation such as heating. It is known that one-part compositions can be obtained. For example, Japanese Patent Laid-Open No. 4-202523 describes a specific example in which a resin containing an episulfide resin is liquefied using a carboxylic acid-containing compound and a thermal latent catalyst as a curing agent. However, since this composition requires 30 minutes at 140 ° C. for the curing time (baking time), an episulfide-based thermosetting one-part composition that can be cured under lower temperature and shorter heating conditions is desired. Japanese Patent Application Laid-Open No. 2004-142133 describes a specific example in which phenol or dicyandiamide is added as a curing agent to a resin containing an episulfide resin, but there is no description about storage stability, and a curing temperature of 170 ° C. is required. It does not indicate low temperature fast curability. In Japanese Patent Nos. 3253919, 3540926, and 2001-342253, it is said that a thermosetting one-part resin composition using an episulfide resin is possible by using a latent curing agent. No specific example is described as to which specific curing agent is used and how much good low temperature fast curing and storage stability can be obtained.
JP-A-50-124952 JP-A-11-140161 JP 2002-173533 A JP-A-4-202523 JP 2004-142133 A Japanese Patent No. 3253919 Japanese Patent No. 3540926 JP 2001-342253 A

In order to solve the above-mentioned problems, the applicant of the present application in Japanese Patent Application No. 2005-039929,
(1) (A) a compound containing two or more thiirane rings in the molecule, (B) a compound containing one or more thiirane rings and oxirane rings in the molecule, and (C) one or more oxiranes in the molecule. One or more compounds represented by the above (A) to (C) of a compound having a ring and not containing a thiirane ring, wherein the content ratio of the oxirane ring / thiirane ring is 80/20 to 0/100 The compound or a mixture of the compounds,
(2) a thiol compound having one or more thiol groups in the molecule;
(3) Heat-latent curing accelerator The thermosetting one-part resin composition containing the above-mentioned (1) to (3) as essential components is faster curing at a lower temperature than the conventional episulfide thermosetting one-part resin composition. It was confirmed that the composition had excellent properties and had good storage stability.

  Therefore, in the present invention, the above-described heat-curable one-component resin composition is further improved, that is, excellent in rapid curability by heating at a low temperature, has high adhesive strength, and causes separation uncured during heat-curing. An object of the present invention is to provide a one-component resin composition having good storage stability (storage stability).

As a result of intensive studies to achieve the above problems, the present inventors
(1) (A) a compound containing two or more thiirane rings in the molecule, (B) a compound containing both a thiirane ring and an oxirane ring in the molecule, and (C) one or more oxirane rings in the molecule. The compound containing one or more compounds represented by the above (A) to (C), and having a oxirane ring / thiirane ring content ratio of 40/60 to 10/90 Or a mixture of the compounds (2) a thiol compound having one or more thiol groups in the molecule (3) a thermal latent curing accelerator (4) a core-shell type acrylic rubber fine particle (5) an acidic compound and / or borate esters The composition comprising (1) to (5) as an essential component is excellent in low-temperature rapid curability, has high adhesive strength, does not cause separation and uncuring during heat curing, and has storage stability (storage stability). Good one-part resin assembly It was found to be an adult product.

  The present invention is one-part, has good storage stability (storage stability), cures rapidly with a low heating temperature, has high adhesive strength, and is tough and has excellent physical properties without causing uncured separation. Can be used as adhesive, casting, molding, painting, coating material, etc. with excellent workability and reliability.

The separation uncured here is a phenomenon that may be seen in the heat-curable one-part resin composition, and the heat-curable one-part resin composition that is solid in the adhesion and impregnation of fine gaps. The heat latent curing accelerator inside is filtered and the resin and curing agent are separated, and the gap portion becomes insufficient due to the curing agent becoming uncured. However, in the present invention, such unseparated uncured material can be suppressed, and therefore, it can be applied particularly to adhesion to fine gaps and for sealing purposes.

Hereinafter, the present invention will be described in detail.
(1) About the resin component containing a thiirane ring The compound (A) containing a thiirane ring used in the present invention may be a compound containing two or more thiirane rings in the molecule. Further, the compound (B) containing a thiirane ring may be a compound containing at least one thiirane ring and one oxirane ring in the molecule. In addition, the compound (A) or (B) containing the thiirane ring may have a functional group other than the oxirane ring and the thiirane ring. Specific examples thereof include a hydroxyl group, a vinyl group, an acetal group, an ester group, a carbonyl group, an amide group, and an alkoxysilyl group. Furthermore, the compound (A) or (B) containing the thiirane ring can be used alone or in admixture of two or more.

  The thiirane ring-containing compound of the present invention is produced by various methods. For example, thermal hydrolysis of hydroxymercaptan, treatment with 1,2-chlorothiol with a weak alkaline solution, treatment with ethylenically unsaturated ethers such as sulfur or polysulfide dialkyl.

  Further, a method for obtaining a thiirane ring-containing compound by replacing all or part of oxygen atoms in an epoxy ring with a sulfur atom using an epoxy compound as a raw material is already known. Such compounds are also called episulfides or episulfide resins. Illustratively, J.M. Polym. Sci. Polym. Phys. 17, 329 (1979), a method using an epoxy compound and thiocyanate, Org. Chem. , 26, 3467 (1961), a method using an epoxy compound and thiourea, a method disclosed in JP-A No. 2000-351829, and JP-A No. 2001-342253, etc., but are not limited thereto. Absent.

  Specific examples of the thiirane ring-containing compound described in detail above include, for example, 2,2-bis (4- (2,3-epithiopropoxy) phenyl) propane, bis (4- (2,3-epithio). Propoxy) phenyl) methane, 1,6-di (2,3-epithiopropoxy) naphthalene, 1,1,1-tris- (4- (2,3-epithiopropoxy) phenyl) ethane, 2,2- Bis (4- (2,3-epithiopropoxy) cyclohexyl) propane, bis (4- (2,3-epithiopropoxy) cyclohexyl) methane, 1,1,1-tris- (4- (2,3- Epithiopropoxy) cyclohexyl) ethane, 2,5-epithiocyclohexyl) ether of 1,5-pentanediol, di (3,4-epithiooctyl) ether of 1,6-hexanediol, etc. Including but not limited to.

  The compound (B) having both a thiirane ring and an oxirane ring in one molecule of the present invention undergoes episulfidation when an epoxy compound is used as a raw material and an oxygen atom in the epoxy ring is exchanged with a sulfur atom to synthesize an episulfide resin. It can be obtained by adjusting the amount of reagent used or reaction conditions. Alternatively, partial episulfides obtained by separation by various purification methods can be obtained by mixing with all episulfides.

  A more preferable thiirane ring-containing compound in the present invention is a hydrogenated (hydrogenated) hydrogenated (hydrogenated) carbon-carbon unsaturated bond of an aromatic ring of an epoxy compound having a bisphenol skeleton as disclosed in JP-A-2000-351829. A compound containing a thiirane ring in which all or part of the oxygen atoms of the oxirane ring of the bisphenol epoxy resin has a sulfur atom, particularly a thiirane ring-containing compound containing a hydrogenated bisphenol A skeleton, and a composition using this compound Is particularly excellent in curability, workability and storage stability.

The compound (C) having one or more oxirane rings in the molecule and not containing a thiirane ring used in the present invention is generally called an epoxy compound. The epoxy compound only needs to have one or more epoxy groups in the molecule. As a commercially available product of this epoxy compound, for example, as a monofunctional epoxy compound, Cardura E10P manufactured by Japan Epoxy Resin Co., Ltd., Denacor EX111, EX121, EX141, EX145, EX146 manufactured by Nagase ChemteX Corporation, KBM403 manufactured by Shin-Etsu Chemical Co., Ltd. However, it is not limited to these. In addition, as an epoxy compound having two or more epoxy groups in the molecule, for example, Epicoat 828, 1001, 801, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, manufactured by Japan Epoxy Resin Co., Ltd. Epicron 830, 835LV, HP4032D, 703, 720, 726, HP820 manufactured by Dainippon Ink Industries, Ltd., EP4100, EP4000, EP4080, EP4085, EP4088, EPU6, EPR4023, EPR1309, EP49-20 manufactured by Asahi Denka Kogyo Co., Ltd. However, it is not limited to these.
These epoxy compounds described above may be used alone or in combination of two or more.
The monofunctional epoxy compound is preferably used for adjusting the properties (for example, viscosity) of the composition and adjusting the crosslinking density of the cured product. An epoxy compound having two or more functional groups is preferably added in order to improve heat resistance and adhesiveness.
In particular, a bisphenol-type epoxy resin is preferable because it is tougher and has a better balance between curability and storage stability.
In addition, each component of above-mentioned (A)-(C) may have functional groups other than an oxirane ring and a thiirane ring. For example, a hydroxyl group, vinyl group, acetal group, ester group, carbonyl group, amide group, alkoxysilyl group and the like.

  The compound represented by (A) to (C) in the composition of the present invention is a compound (A) containing two or more thiirane rings in the molecule, or one both a thiirane ring and an oxirane ring in the molecule. The compound (B) containing one or more of the compounds (C) having one or more oxirane rings in the molecule and not containing a thiirane ring, wherein the ratio of the number of oxirane rings / thiirane rings is 40 / 60 to 10/90, or a mixture of the compounds. When the content ratio of the thiirane ring is smaller than this range, sufficient rapid curability cannot be expressed. When a compound containing an oxirane ring is present, the solubility of the latent curing agent is improved, and as a result, the curing rate is further improved.

(2) About the thiol compound which has one or more thiol groups in a molecule The thiol compound used for this invention should just be a thiol compound which has one or more thiol groups in a molecule | numerator. Specifically, 3-methoxybutyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, tridecyl 3-mercaptopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopro Pionate, methylthioglycolate, 2-ethylhexylthioglycolate, ethylene glycol bisthioglycolate, 1,4-butanediol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, di ( 2-mercaptoethyl) ether, 1-butanethiol, 1-hexanethiol, cyclohexyl mercaptan, 1,4-butanedithiol, 3-mercapto-2-butanol, γ-mercapto Pyrtrimethoxysilane, benzenethiol, benzyl mercaptan, 1,3,5-trimercaptomethylbenzene, 1,3,5-trimercaptomethyl-2,4,6-trimethylbenzene, terminal thiol group-containing polyether, terminal thiol Examples include, but are not limited to, group-containing polythioethers, thiol compounds obtained by reaction of epoxy compounds with hydrogen sulfide, and thiol compounds having terminal thiol groups obtained by reaction of polythiol compounds with epoxy compounds. .

Examples of commercially available thiol compound products include Epomate QX11, QX12, EpiCure QX30, QX40, QX60, QX900, Capcure CP3-800 manufactured by Japan Epoxy Resin Co., Ltd., OTG, EGTG, TMTG manufactured by Sakai Chemical Co., Ltd. Examples include, but are not limited to, PETG, 3-MPA, TMTP, PETP, Toyo Fine Chemical Co., Ltd. Thiocol LP-2, LP-3, Polythiol QE-340M, Shin-Etsu Chemical Co., Ltd. KBM803, and the like. These may be used alone or in admixture of two or more.
More preferable thiol compounds are those having as few basic impurities as possible from the viewpoint of storage stability. From the viewpoint of heat resistance of the cured product, a thiol compound having 2 or more functional groups and a thiol compound containing an aromatic ring in the molecule are more preferable.

  Although there is no restriction | limiting in particular about the compounding quantity of the thiol compound in the composition of this invention, Preferably it is 0.01-0. 0 by thiol equivalent ratio with respect to the sum total of the thiirane ring and oxirane ring in the resin component of the said (1) description. It can be added within the range of 5. When a thiol compound is added within the above-mentioned range, the curing rate and storage stability can be further improved, and a composition excellent in the balance between the strength and heat resistance of the cured product can be obtained.

(3) Thermal latent curing accelerator The thermal latent curing accelerator used in the present invention has no activity on epoxy resins at room temperature, and is activated and accelerated by dissolution, decomposition, transition reaction, etc. by heating. It is a compound that functions as an agent. Examples include, but are not limited to, imidazole compounds and derivatives thereof that are solid at room temperature, salts of various amines and acids, solid dispersion-type amine adduct-based latent curing accelerators, and the like. Further, examples of solid dispersion type amine adduct-based latent curing accelerators include reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems) and reaction products of amine compounds with isocyanate compounds or urea compounds ( Urea type adduct system) and the like, but are not limited thereto. Of these thermal latent curing accelerators, preferably, a solid dispersion type amine adduct based latent curing accelerator, more preferably a urea type adduct based thermal latent curing accelerator, has a low curing temperature of the composition of the present invention. Demonstrates excellent storage stability. The blending amount of these thermal latent curing accelerators is not particularly limited, but is preferably added in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the total resin component of (1). The When there are few hardening accelerators, hardening will be slow, and when too much, storage stability will worsen.

  Examples of products that are commercially available as the thermal latent curing accelerator include imidazole compounds 2PZ, 2PHZ, 2P4MHZ, C17Z, 2MZ-A, 2E4MZ-CNS, 2MA-OK, and Ajinomoto Fine Techno Co., Ltd. manufactured by Shikoku Kasei Kogyo Co., Ltd. Company Amicure PN23, PN31, PN40J, PN-H, MY24, MY-H, Asahi Denka Co., Ltd. EH-3293S, EH-3366S, EH-3615S, EH-4070S, EH-4342S, EH-3331S, Asahi Kasei Chemicals Examples include NOVACURE HX-3742, HX-3721, manufactured by Fuji Chemical Industry Co., Ltd., FXE-1000, FXR-1030, FXR-1080, FXR-1110, and the like, but are not limited thereto.

(4) Core-shell type acrylic rubber fine particles The core-shell type acrylic rubber fine particles used in the present invention are fine particles which are polymers having different properties in the core part and the shell part of the particle. Many examples of such materials include core-shell type fine particles comprising a rubbery polymer core and a glassy polymer shell. The core-shell structured particles have “elasticity” in the core portion and “hardness” in the shell portion, and do not dissolve in the liquid resin. In the present invention, by adding the core-shell type acrylic rubber fine particles, high adhesive strength and thermal shock resistance at low temperature after curing can be imparted, and separation uncured can be suppressed.

  In the production of the preferred powder particles used in the present invention, the powder particles are first produced by polymerizing a polymerizable monomer as a core portion. Examples of this polymerizable monomer include (meth) acrylate monomers such as n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-decyl (meth) acrylate, styrene, vinyl Aromatic vinyl compounds such as toluene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, vinylidene cyanide, 2-hydroxyethyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2- Examples include hydroxyethyl fumarate, hydroxybutyl vinyl ether, monobutyl maleate, butoxyethyl methacrylate, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, Reactions such as tyrolpropane di (meth) acrylate trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, hexanediol tri (meth) acrylate, oligoethylenedi (meth) acrylate, oligoethylenetri (meth) acrylate Crosslinkable monomers having two or more functional groups, aromatic divinyl monomers such as divinylbenzene, triallyl trimellitic acid, triallyl isocyanate, and the like. These may be used alone or in combination of two or more.

  The rubber properties vary depending on the molecular weight, molecular shape, and crosslinking density of the polymer obtained by polymerizing the polymerizable monomer. In the present invention, the core portion must be a rubbery polymer at room temperature (eg, 25 ° C.). More preferably, the obtained polymer has a glass transition point of −10 ° C. or lower.

  Next, a second polymerization is performed in which the polymer particles thus obtained are used as a core, and a polymerizable monomer is further polymerized to form a shell made of a polymer having glass properties at room temperature. The polymerizable monomer used in this case can be selected from the same polymerizable monomers as those for obtaining the core. However, in the present invention, the shell portion must be a glassy polymer at room temperature (eg, 25 ° C.). Preferably, the glass transition point of the obtained polymer is preferably 70 ° C. or higher. This can be determined by the molecular weight, molecular shape, crosslink density, etc. of the polymer obtained when the selected polymerizable monomer is copolymerized. When it is not glassy at room temperature, when the polymer particles are mixed with a liquid resin capable of radical polymerization to form a sealant composition, the particles are swollen by the radically polymerizable monomer and stored during storage. The viscosity increases with time and gels. That is, the storage stability becomes insufficient.

Preferable examples of the polymerizable monomer used as the shell material include (meth) acrylates having 1 to 4 carbon atoms in the alkyl group, such as ethyl (meth) acrylate, n-butyl acrylate, methyl methacrylate, and butyl methacrylate. . One of these may be used, or two or more may be used in combination. Among these, methyl methacrylate is particularly preferable.
The particle diameter of these core-shell type acrylic rubber fine particles is preferably in the range of 0.05 μm to 10 μm. If it is smaller than 0.05 μm, high adhesive strength cannot be obtained, and if it exceeds 10 μm, the toughness of the cured product (the balance of the sea-island structure is lost) cannot be obtained.

  As such core-shell type acrylic rubber fine particles, for example, F351 manufactured by Zeon Corporation, Metabrene S manufactured by Mitsubishi Rayon Co., Ltd. and Staphyloid manufactured by Gantz Kasei Co., Ltd. (all trade names) are commercially available. In addition, Acryset BPF-307 manufactured by Nippon Shokubai Co., Ltd., in which core-shell type acrylic rubber fine particles are uniformly dispersed in an epoxy resin, is also commercially available. However, the core-shell type acrylic rubber fine particles are not limited to these.

  The core-shell type acrylic rubber fine particles are contained in such an amount that gives good properties to the cured adhesive composition. Specifically, it is used in the range of 1 to 50 parts by weight with respect to 100 parts by weight as the total of component (1). When the amount is less than 1 part by weight, sufficient reduction in adhesion force and measures against uncured separation cannot be obtained sufficiently, and when it exceeds 50 parts by weight, workability tends to deteriorate due to decrease in adhesion force and increase in viscosity.

(5) Acidic compounds and / or boric acid esters The acidic compounds and / or boric acid esters used in the present invention serve to block the basicity of the surface of the curing accelerator by reacting with the surface of the curing accelerator. There is an effect of further improving the storage stability of the composition in the storage state.

  The acidic compound is a liquid or solid organic acid or inorganic acid at room temperature. Examples thereof include, but are not limited to, sulfuric acid, acetic acid, adipic acid, tartaric acid, fumaric acid, barbituric acid, boric acid, pyrogallol, phenol resin, carboxylic acid anhydride and the like.

  Boric acid esters are boric acid esters that are liquid or solid at room temperature. For example, 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, trinonyl borate Decyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxaundecyl) (1,4,7,10, 13-pentaoxatetradecyl) (1,4,7-trioxaundecyl) borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, etc. Not but be under it is not limited to this.

  These (5) acidic compounds and / or borate esters may be used alone or in admixture of two or more. Moreover, you may add as a storage stability improver what mixed these acidic substances, an epoxy resin, etc., and made into a masterbatch. Examples of such storage stability improvers include, but are not limited to, commercially available products such as Shikoku Kasei Kogyo Cure Duct L-07N. The blending amounts of these acidic substances and boric acid esters are not particularly limited, but are preferably added in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin component (1). The storage stability is further improved by addition, but if the addition amount exceeds 10 parts by weight, the curability is lowered, and if it is less than 0.01 part by weight, no effect is recognized.

  In the heat-curable one-part resin composition of the present invention, pigments, dyes and other colorants, inorganic fillers such as calcium carbonate, talc, silica, alumina and aluminum hydroxide, as long as the characteristics of the present invention are not impaired, An appropriate amount of additives such as a flame retardant, an organic filler, a plasticizer, an antioxidant, an antifoaming agent, a coupling agent, a leveling agent, and a rheology control agent may be blended. By these additions, a composition excellent in resin strength, adhesive strength, flame retardancy, thermal conductivity, workability and the like and a cured product thereof can be obtained.

  The heat-curable one-component resin composition of the present invention is a one-component, has a good storage stability, forms a cured product that rapidly cures at a low heating temperature, exhibits toughness and excellent physical properties, and has high adhesive strength. It is useful for adhesion, casting, molding, painting, coating agent, etc. with excellent workability and reliability.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the following examples. Further, the blending ratios in the following table are based on weight unless otherwise specified.

The materials used in the examples are as follows.
Compound A: 100% episulfide product of hydrogenated bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd. Compound B: 80% episulfide product of hydrogenated bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd. Denacol EX146: P-tertiary butylphenyl glycidyl ether / acreset BPF-307 manufactured by Nagase ChemteX Corporation: core shell type acrylic rubber fine particle dispersed epoxy resin manufactured by Nippon Shokubai Co., Ltd. (rubber component content 16% by weight)
・ Epicoat 807: Bisphenol F type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd. ・ EpiCure QX30: Trifunctional aliphatic polythiol manufactured by Japan Epoxy Resin Co., Ltd. FXR-1080: Latent curing agent Fuji Cure manufactured by Fuji Kasei Kogyo Co., Ltd. F351: Japan Core shell type acrylic rubber fine particles manufactured by ZEON Co., Ltd./L-07N: Cure duct manufactured by Shikoku Kasei Kogyo Co., Ltd. (organic acid preservative improver)

(Examples 1-8 and Comparative Examples 1-8)
The materials were mixed and stirred at a weight ratio as shown in Table 1 below to obtain each sample (composition) of Examples 1 to 8 and Comparative Examples 1 to 8. Each sample obtained was evaluated for the following items. The results are also shown in Table 1.

The measurement method for each item is described below.
[Thiirane ring content]
The thiirane ring content of the resin component (1) was determined by calculation of the following formula.
Thiirane ring content (%) = thiirane equivalent of resin component (1) / (thiirane equivalent of resin component (1) + oxirane equivalent of resin component (1)) × 100
[80 ° C gel time and curing time]
0.1 g of each composition is dropped on a hot plate set at 80 ° C., the time until the composition does not flow even when touched by the gel time, the time until the composition becomes hard and the surface tack is eliminated is the curing time [Shear bond strength]
A 1.6 × 25 × 100 mm SPCC-SD steel plate is coated and bonded to a 10 mm overlapped surface, and cured for 30 minutes in a thermostatic bath set at 80 ° C. and then universal at 25 ° C. Tensile speed 10 mm / min. Measured with
[Hardened material brittleness]
The state of the composition cured product after the shear bond strength test was observed, and the case where the cured product was broken in a crushed state was brittle (x), and the case where the cured product was not broken was regarded as tough (◯).
[−20 ° C. storage stability]
About 30 ml of each composition was put in a 50 ml glass bottle, sealed, stored in a cool box set at −20 ° C., and the time until the viscosity at 25 ° C. doubled the initial value was determined.
[Addition amount of rubber fine particles]
The addition amount (parts by weight) of the rubber fine particle component relative to a total of 100 parts by weight of the liquid components in the resin component (1) was used.
[Separated uncured]
The composition is dropped into the center of the slide glass so as to be a hemisphere having a diameter of 1 mm, and another slide glass is overlaid and fixed with a pinch or the like. After standing for 2 minutes, it was cured for 30 minutes in a thermostat set at 80 ° C., and it was observed whether separation of uncured resin components occurred at the outer peripheral edge of the cured composition.

Table 1

  In Examples 1 to 6, a thiol compound and a thermal latent curing accelerator are added to the resin component in which the content ratio of the oxirane ring / thiirane ring in the mixture of the resin component (1) is in the range of 40/60 to 10/90. , Core-shell type acrylic rubber fine particles and an acidic compound have a high shear bond strength of 15 MPa or more, a curing time at 80 ° C. is within 15 minutes, and storage at −20 ° C. for 3 months or more. A resin composition having stability and no separation uncured was obtained.

  In Comparative Examples 1 and 3, it can be seen that when the content of the thiirane ring in the mixture of the resin component (1) is less than 60, rapid curability within 15 minutes cannot be achieved at 80 ° C. In Comparative Examples 2 and 6, it can be seen that when the content of the thiirane ring in the mixture of the resin component (1) is greater than 90, high shear adhesive strength of 15 MPa or more and good storage stability of 3 months or more cannot be achieved. Moreover, in Comparative Examples 3-6, when a core-shell type acrylic rubber microparticle is not included, it turns out that isolation | separation non-hardening will generate | occur | produce.

  In Examples 7 and 8, even when the type of the core-shell type acrylic rubber fine particles was changed, the shear-bonding strength was high at 15 MPa or more, the curing time at 80 ° C. was within 15 minutes, and at −20 ° C. A resin composition having a storage stability of 3 months or longer and free from separation and uncuring was obtained.

  In Comparative Example 7, even when the type of the core-shell type acrylic rubber fine particles is changed, if the content of the thiirane ring in the mixture of the resin components (1) and (2) is smaller than 60, rapid curing within 15 minutes at 80 ° C. It can be seen that sex cannot be achieved. In Comparative Example 8, even when the type of the core-shell type acrylic rubber fine particles is changed, if the content of the thiirane ring in the mixture of the resin components (1) and (2) is greater than 90, a high shear bond strength of 15 MPa or more and 3 It can be seen that good storage stability for more than a month cannot be achieved.

  The present invention is excellent in workability and reliability, and can be used as adhesion, sealing, casting, molding, coating, coating material, etc. for transportation equipment, electrical equipment, electronic equipment industry, etc., especially at low heating temperature. It is useful as an adhesive / sealant for mounting and assembling electronic components that require a fast curing property.

Claims (6)

A thermosetting one-component resin composition comprising (1) to (5) as essential components.
(1) The above compound or a mixture of the above compounds comprising one or more compounds represented by the following (A) to (C), wherein the content ratio of the oxirane ring / thiirane ring is 40/60 to 10/90 ( no oxirane ring with having two or more thiirane rings in a) the molecule has compound (B) both thiirane ring and oxirane ring 1 or more in a molecule having a hydrogenated bisphenol skeleton, a hydrogenated Compound (C) having bisphenol skeleton (C) Compound having one or more oxirane rings and no thiirane ring (2) Thiol compound having one or more thiol groups in the molecule (3) Solid dispersed amine adduct -Based latent curing accelerator (4) Core-shell type acrylic rubber fine particles (5) Boric acid esters The component (3) is 0.1 to 30 parts by weight, the component (4) is 1 to 50 parts by weight, and the component (5) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the component (1) . Furthermore, the amount of component (2) added is 0.01 to 0.5 in terms of thiol equivalent ratio with respect to the total of thiirane and oxirane rings in component (1). One-part resin composition. The thermosetting one-component resin composition according to claim 1, wherein the compound (C) having one or more oxirane rings in the molecule and not containing a thiirane ring is a compound having a bifunctional or higher functional oxirane ring. . The thermosetting one-component resin composition according to any one of claims 1 to 3 , wherein the compound having an oxirane ring is an epoxy compound.
The heat-curable one-part resin composition according to any one of claims 1 to 4, wherein the solid dispersion type amine adduct-based latent curing accelerator is a urea-type adduct-based thermal latent curing accelerator.
(4) The core portion of the core-shell type acrylic rubber fine particles is a rubbery polymer having a glass transition point of −10 ° C. or lower, and the shell portion is a glassy polymer having a glass transition point of 70 ° C. or higher. The thermosetting one-component resin composition described.