JPH04132789A - Curable type tacky agent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing a silicon-containing organic polymer, an epoxy resin, a tackifier resin, a silanol condensation catalyst and a curing agent, etc., at a specific ratio and capable of providing excellent tacky and bonding characteristics at ambient temperature in a relatively short time. CONSTITUTION:The objective composition containing (A) 100 pts.wt. organic polymer such as a polyether having >=1 hydrolyzable silicon-containing groups or silanol groups, (B) 1-300 pts.wt. epoxy resin, (C) 1-300 pts.wt. tackifier resin, (D) 0.01-10 pts.wt. silanol condensation catalyst, (E) a curing agent in an amount corresponding to the epoxy equiv. of the component (B) for epoxy resins and (F) 0-100 pts.wt. curing regulating agent such as a carboxylic acid or a beta- diketone.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a curable pressure-sensitive adhesive composition that provides excellent adhesive and adhesive properties at room temperature in a relatively short period of time.

[Prior Art] Conventional adhesives can be roughly divided into solvent-based adhesives, water-based adhesives, and hot-melt adhesives. However,
Common problems among these include the inability to obtain strong adhesive strength, poor heat resistance and creep resistance, and insufficient adhesion and adhesive properties. In addition, there have recently been reports of curable adhesives, which are polymeric materials that can be applied at room temperature and are cured using ultraviolet rays, electron beams, heat, etc. It is. However, these disadvantages include the cost and space required for drying equipment and curing equipment, and the processing speed also requires a long time.

[Problems to be Solved by the Invention] The present invention solves the problem that solvent-based adhesives, water-based adhesives, and hot-melt adhesives do not have strong adhesive strength and have poor adhesive properties such as poor heat resistance and creep resistance. In addition, UV-curable adhesives, electron beam-curable adhesives, and heat-curable adhesives require expense and space for drying equipment and curing equipment, and the processing speed also requires a long time. This was done to solve the problems of the prior art.

[Means for Solving the Problems] The present invention solves the above-mentioned problems of the prior art, and enables
The curable adhesive composition of the present invention was made to provide a curable adhesive composition that provides excellent adhesive properties and adhesion properties in a relatively short period of time, and the curable adhesive composition of the present invention comprises (a) 100%
Organic polymers having at least one hydrolyzable silicon-containing group or silanol group in parts by weight of the molecule, (b) 1-
300 parts by weight of epoxy resin, (c) 1 to 300 parts by weight of tackifying resin, (d) 0.01 to 10 parts by weight of silanol condensation catalyst, (e) an amount corresponding to the epoxy equivalent of the epoxy resin used. Curing agent for epoxy resin and (f)0
It is characterized by containing ~100 parts by weight of a hardening modifier as an active ingredient.

At least 1 in the molecule of component (a) used in the present invention
When a polyether is used as an organic polymer having two hydrolyzable silicon-containing groups or silanol groups, the main chain of the polyether essentially has the general formula -R' -0-
(In the formula, R1 represents a divalent hydrocarbon group having 2 to 4 carbon atoms.) Those having a repeating unit represented by the formula are preferred.

Examples of such organic polymers include MS polymers manufactured by Kanekabuchi Chemical Co., Ltd., such as MS300 and MS2.
OA and Cy9le (registered trademark), such as Cy9le 5B2
5, Cy9le 5B30, etc. are commercially available.

At least 1 in the molecule of component (a) used in the present invention
The organic polymer having two hydrolyzable silicon-containing groups or silanol groups is preferably one copolymerized with a monomer whose main chain is essentially an acrylic ester, manufactured by Kanekabuchi Chemical Co., Ltd. For example,
It is commercially available as Cy9le 5A01 and Cy9le M400.

These organic polymers as component (a) may be used alone or in combination of two or more types depending on the viscosity and physical properties of the cured product.

Examples of the epoxy resin as component (b) used in the present invention include novolac type epoxy resin, epichlorohydrin bisphenol A type epoxy resin, epichlorohydrin bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, urethane-modified epoxy resin, etc. Examples include, but are not limited to, alicyclic epoxy resins, and any generally known epoxy resin can be used. These epoxy resins contain at least one epoxy group represented by the general formula: % formula % in their molecules, and can be crosslinked or polymerized in the presence of a curing agent or with amino groups in their own molecules. Among the above, particularly preferred are novolac type epoxy resin, epichlorohydrin bisphenol A type epoxy resin, epichlorohydrin bisphenol F type epoxy resin, and urethane-modified epoxy resin.

These epoxy resins may be used alone, or two or more types may be used in combination, depending on the working conditions, physical properties of the cured product, and the like.

The amount of the epoxy resin used as the component (b) used in the present invention is as follows:
1 to 300 parts by weight, preferably 5 to 100 parts by weight, per 100 parts by weight of component (a), an organic polymer having at least one hydrolyzable silicon-containing group or silanol group in the molecule. It is. If the amount used is less than 1 part by weight, the cohesive force of the cured product will be low and high adhesive strength will not be obtained, and if it exceeds 300 parts by weight, the cured product will become brittle.

The tackifier resin which is component (c) used in the present invention is a commonly used tackifier resin, such as natural resin, rosin, modified rosin, modified rosin derivative, polyterpene resin, aromatic resin, etc. Petroleum resins, phenolic resins, alkylphenol acetylene resins, styrene resins, xylene resins, coumaron indene resins, vinyltoluene-α-methylstyrene copolymers, acrylic acid copolymer resins, vinyl acetate resins, etc. but,
It is not limited to these.

These tackifier resins may be used alone or in combination of two or more types depending on performance and working conditions.

The amount of the tackifying resin used as the component (c) used in the present invention is as follows:
1 to 300 parts by weight, preferably 5 to 100 parts by weight, per 100 parts by weight of component (a), an organic polymer having at least one hydrolyzable silicon-containing group or silanol group in the molecule. range. If the amount used is less than 1 part by weight, initial tackiness cannot be obtained, and if it exceeds 300 parts by weight, the cured product will become brittle.

The silanol condensation catalyst used as component (d) used in the present invention is a commonly used silanol condensation catalyst, such as dibutyltin monophthalate, dibutyltin siphthalate, dibutyltin monolaurate, dibutyltin dilaurate, and dibutyltin monomaleate. , dibutyltin dimaleate, carboxylic acid salts such as tin octylate, alkyl titanates, acetylacetone metal salts such as tin acetylacetone, aluminum acetylacetonate, hot melts of dibutyltin ogicide and dioctyl phthalate (DOP), various metal chelates. Examples include, but are not limited to. Further, two or more types of these silanol condensation catalysts may be used in combination for the purpose of adjusting the curability of the curable pressure-sensitive adhesive composition.

The amount of the silanol condensation catalyst used in the present invention as component (d) is based on 100 parts by weight of the organic polymer having at least one hydrolyzable silicon-containing group or silanol group in the molecule as component (a). , in the range of 0.01 to 10 parts by weight. If the amount used is less than 0.01 parts by weight, the catalytic effect will be low, resulting in poor curing, and if it exceeds 10 parts by weight, curing will be rapid and coating properties on adherends will be poor.

Examples of the curing agent for epoxy resin as component (e) used in the present invention include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, benzyldiethylamine, dimethylaminomethylphenol, trimethylaminomethylphenol, Pyridine, piperidine, metaphenylenediamine, trifluoroboronomonoethylamine,
Examples include, but are not limited to, amines, imidazoles, phenolic resins, melamine resins, dicyandiamide, polysulfides, polymercaptans, guanidine, ketimine, and silamine.

The amount of curing agent for epoxy resin used as component (e) is as follows: (b)
The required amount of curing agent corresponding to the epoxy equivalent of the component epoxy resin may be used.

The curing regulator, component (f), used in the present invention is as follows:
Examples include carboxylic acids or those that produce carboxylic acids through reaction. For example, carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, n-valeric acid, isovaleric acid, ethylmethylacetic acid, trimethylacetic acid, caproic acid, caprylic acid, capric acid, lauric acid, monochloroacetic acid, dichloroacetic acid. , trichloroacetic acid, 2-monochloropropionic acid, 3-monochloropropionic acid, p-chlorobenzoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, benzoic acid, toluic acid, 1-naphthoic acid , 2-naphthoic acid,
Monocarboxylic acids such as 0-salicylic acid; dicarboxylic acids such as oxalic acid, malonic acid, cono-phosphoric acid, glutaric acid, adipic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, and terephthalic acid; polycarboxylic acids such as mellitic acid; carboxylic acids, but are not limited to these.

In addition, acid anhydrides that produce carboxylic acids by reaction include acetic anhydride, benzoic anhydride, acetic acid-propionic acid mixed anhydride, phthalic anhydride, co/% phosphoric anhydride, maleic anhydride, and mellitic anhydride. substance; formic acid methyl ester,
Formic acid ethyl ester, acetic acid methyl ester, acetic acid ethyl ester, acetic acid n-propyl ester, acetic acid n-butyl ester, propionic acid ethyl ester, butanoic acid ethyl ester, pentanoic acid ethyl ester, hexanoic acid ethyl ester, benzoic acid methyl ester, benzoic acid Carboxylic acid esters such as acid ethyl ester, acetic acid phenyl ester, 〇-salicylic acid methyl ester, oxalic acid diethyl ester, malonic acid dimethyl ester, and vinyl acetate; halogenated acids such as acetyl chloride, propanoyl chloride, benzoyl chloride, and phenylacetyl chloride. Examples include, but are not limited to, acyls. In addition, examples of substances that give the same effect as carboxylic acids include β-acetyl acetone, etc.
Examples include diketones, but the present invention is not limited thereto, and any generally used vulcanization retarder can be used. Depending on workability and curing conditions, these curing modifiers may be used alone, or
Two or more types may be used in combination.

The amount of the curing modifier used as component (f) is 0 to 100 parts by weight based on 100 parts by weight of the organic polymer having at least one hydrolyzable silicon-containing group or silanol group in the molecule, which is component (a). Parts by weight, preferably in the range from 0 to 50 parts by weight.

The curable pressure-sensitive adhesive composition of the present invention requires moisture management of the composition, and a latent curing agent among the curing agents for epoxy resin as component (e), such as dicyandiamide, 3
By using boron fluoride amine complexes, ketimines, silaminos, dihydrazides, amine microcapsules, amine zeolite adsorbates, etc., a one-component curable adhesive composition can be obtained.
Furthermore, by appropriately combining the above six components (a) to (f), a two-component thermal curable pressure-sensitive adhesive composition can be obtained. Furthermore, if a high molecular weight epoxy resin that is solid at room temperature is used as the epoxy resin as component (b), it can also be used as a hot melt type curable adhesive composition.

In the curable adhesive composition of the present invention, in addition to the above six components, resins, various fillers, plasticizers, anti-aging agents,
Additives such as ultraviolet absorbers, adhesion promoters, pigments, foaming agents, and dehydrating agents may be added as necessary. For example, when fillers are used as additives, fillers such as glass fiber, mica, wood flour, asbestos, calcium carbonate, magnesium carbonate, titanium oxide, carbon black, silica, clay talc, quartz, copper powder, silver powder, etc. Various metal powders can be effectively used. In addition, organic solvents and thixotropic agents may be used depending on workability, and application methods such as brush application, spatula application, hand roller application, trowel application, spray application, and roll spreader dispenser may be used. I can do it.

[Function] The curable adhesive composition of the present invention containing each of the components shown above initially acts as an adhesive to fix the adherend,
After that, the organic polymer and epoxy resin having at least one hydrolyzable silicon-containing group or silanol group in the molecule are cured by a silanol condensation catalyst and a curing agent for epoxy resin, resulting in strong and heat-resistant properties. Provides good adhesion. Furthermore, by using an appropriate amount of a curing modifier, one-component composition can be achieved relatively easily.

[Example] Example 1 25 g of methyl ethyl ketone and 25 g of YS Polyster T145 (polyterpene tackifier resin manufactured by Yasushi Oil Co., Ltd.) were charged into a four-piece Locolben and dissolved with stirring. 25 g of epichlorohydrin bisphenol A type dipoxy resin) was added and stirred and dissolved again. When this is heated under a nitrogen stream to remove methyl ethyl ketone,
A clear and viscous liquid containing YS Polyster T145 and Epicoat 828 was obtained.

100 g of MS Polymer MS300 (modified silicone resin manufactured by Kanekabuchi Chemical Co., Ltd.) was added to 50 g of this mixture, mixed and stirred, and then 3 g of diethylenetriamine (curing agent for epoxy resin), N-(2-aminoethyl) 3-
Aminopropyltrimethoxysilane (adhesion promoter) 2g
1 and 1 g of dibutyltin dilaurate (silanol condensation catalyst) were added and mixed well, and then coated uniformly to a thickness of 50 μm on a 0.3 mm thick PET (polyethylene terephthalate) film whose surface had been degreased with methanol. The two coated PET films were bonded together with an open time of 10 minutes (20° C.). The peel adhesion strength of this bonded PET film was measured immediately after and after 7 days in accordance with JIS K6854, and it was found to be 1.4 kg/1 nch (strength immediately after) and 7.3 k
A curable pressure-sensitive adhesive composition with excellent initial tackiness and adhesiveness over time of g/1 nch (strength after 7 days) was obtained.

Comparative Example I A composition was prepared under exactly the same conditions as in Example 1, except that YS Polyster T145 was not used.
When applied to a PET film in the same manner as above and measuring the peel adhesion strength, Okg/1nch (strength immediately after),
Although it had oral adhesiveness of 6.7 kg/1 nch (strength after 7 days), it was found that there was no initial adhesiveness at all.

Examples 2 to 4 and Comparative Examples 2 to 3 Modified silicone resins, tackifying resins, epoxy resins, silanol condensation catalysts, curing agents for epoxy resins, curing modifiers, and the types and amounts (g) shown in Table 3. A curable adhesive composition was prepared using an adhesion promoter, and a planar-finished bar (length 30 mm x width 25 mm x thickness 10 mm) was prepared.
), the two coated bars were bonded together with an open time of 10 minutes (20℃), and then pressed for 30 seconds with a load of 150g/cm2 at 20℃. It was cured for 7 days. This pasted bar material conforms to JIS K6852, 20.
Compression shear bond strength was measured at each temperature of 60, 70, and 80°C (Examples 2 to 4).

Comparative Example 2 is the same as Example 1 except that Epicoat 828 is not used.
Comparative Example 3 used a commercially available chloroprene rubber adhesive. 1st
The table shows the types and proportions of the ingredients in the composition (indicated in g) and the measurement results of the compressive shear joint strength.

From the measurement results in Table 1, the compositions of the present invention in Examples 2 to 4 are not significantly affected by temperature in the range of 20 to 80°C and exhibit good heat-resistant adhesion, but Comparative Example 2 It can be seen that compositions No. 3 and 3 have low normal adhesive strength or even lower heat-resistant adhesive strength. Furthermore, regarding heat deterioration resistance, it can be seen that the compositions of Examples 2 to 4 show no deterioration at all, while the compositions of Comparative Examples 2 and 3 show progress in deterioration.

Examples 5-6 Instead of diethylenetriamine, ketimine consisting of diethylenetriamine and methyl isobutyl ketone was used, and the central imino group was reacted with monoepoxide, and N
A composition was prepared in exactly the same manner as in Example 1 except that 3-glycidoxypropyltrimethoxysilane was used instead of -(2-aminoethyl)3-aminopropyltrimethoxysilane, and a curing modifier was added. 1g of octylic acid as
1. The curable adhesive composition of Example 5 was prepared by adding 3 g of vinyltrimethoxysilane as a dehydrating agent, 20 g of acetylacetone as a curing regulator, 40 g of methyl ethyl ketone as a solvent, 20 g of n-hexane, and 20 g of toluene. The curable pressure-sensitive adhesive composition of Example 6 was prepared by placing the compositions of Examples 5 and 6 in a glass bottle with a lid, storing the bottle at 60°C for 7 days, and examining the viscosity stability and adhesive force stability. The results are shown in Table 2.

Table 2 Note) Viscosity measurement method: Single cylinder rotational viscometer Normal strength measurement method: Compression shear adhesive strength, 20
Cure for 7 days [Effects of the Invention] When the curable adhesive composition of the present invention is used for bonding work, it has poor heat resistance and creep resistance, which are the drawbacks of conventional adhesives. Adhesive properties such as low adhesive strength,
Inadequacies in adhesive properties can be improved. Furthermore, by appropriately blending the curable adhesive composition of the present invention, it can be made into a one-component curable adhesive composition, which is easy to handle.

Applicant's agent: Patent attorney Takehiko Suzue

Claims (5)

[Claims] (1) (a) 100 parts by weight of an organic polymer having at least one hydrolyzable silicon-containing group or silanol group in the molecule; (b) 1 to 300 parts by weight of an epoxy resin; (c) 1 to 300 parts by weight parts of the tackifying resin, (d) 0.01 to 10 parts by weight of a silanol condensation catalyst, (e) a curing agent for epoxy resin in an amount corresponding to the epoxy equivalent of the epoxy resin used, and (f) 0 to 100 parts by weight. A curable adhesive composition comprising a curing regulator as an active ingredient. (2) The organic polymer of (a) essentially has the general formula -R^1-O- (wherein R^1 is a divalent hydrocarbon group having 2 to 4 carbon atoms) as the main chain. The curable pressure-sensitive adhesive composition according to claim 1, which is a polyether having a repeating unit represented by the following formula. (3) The curable pressure-sensitive adhesive composition according to claim 1, wherein the organic polymer (a) is obtained by having an acrylic acid ester monomer as the main chain. (4) The curable pressure-sensitive adhesive composition according to claim 1, wherein the curing regulator (f) is a carboxylic acid or one that generates a carboxylic acid through reaction. (5) The curable adhesive composition according to claim 1, wherein the curing regulator (f) is a compound belonging to β-diketones.