JP2001055553A - Adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new adhesive composition having improved adhesion. SOLUTION: This adhesion composition is constituted by (A) 100 pts.wt. polymer having a group of -Si(R1)(OR2)2 (wherein R1 and R2 are each a 1-20C hydrocarbon group which may have a substituent); (B) 1-50 pts.wt., based on 100 pts.wt. component (C), epoxy resin having a group of -R3-O- (wherein R3 is a 2-4C alkylene group); (C) 5-200 pts.wt., based on 100 pts.wt. component (A), epoxy resin excluding component (B); (D) 0.1-20 pt.wt. based on 100 pts.wt. component (A), silanol condensation catalyst; (E) 0.1-20 pts.wt., based on 100 pts.wt. sum of components (B) and (C), epoxy resin curing agent; and (F) a silicon compound having a functional group reactive with the epoxy resins and a group of -Si(OR4)3 (wherein R4 is a 1-20C hydrocarbon group which may have substituent) at a weight retio of a sum of components (A), (B), and (C) to component (F) of 100/0.1 to 100/20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel adhesive composition having improved adhesive strength, and more particularly to an adhesive composition having improved adhesive strength for olefin-based plastics and acrylic-based plastics. I do.

[0002]

2. Description of the Related Art Vinyl chloride plastic (resin)
Has been widely used in various fields because of its advantages of being inexpensive, excellent in processability, and flame retardant. However, in recent years, it has become clear that vinyl chloride plastics have problems related to the global environment, such as the generation of highly toxic substances such as dioxin when incinerated during disposal and the inclusion of plasticizers. Was. Accordingly, the amount of vinyl chloride plastic used has decreased, and instead, olefin plastics that are environmentally friendly and do not generate harmful substances such as dioxin when incinerated have been used.

[0003] However, since olefin-based plastics are non-polar, their surface coatability is inferior to that of polar vinyl chloride-based plastics, so that they are essentially difficult to bond with an adhesive. . Solvent chloroprene-based adhesives are known as adhesives for olefin-based plastics, but use of (organic) solvents and chloroprene contains chlorine, so these uses pose problems related to the global environment. Yes. A hot-melt adhesive which is heated and used as an adhesive for olefin-based plastics is known, but this adhesive has a problem that it cannot be easily used at room temperature.

[0004] Epoxy adhesives are known as typical adhesives for metals and plastics, which are almost universal and are generally used for testing the bonding of new materials. However, the epoxy resin has a problem that a cured product formed is brittle and has low peel adhesion. There are various reports on adhesives that improve the brittleness of cured epoxy resin and improve peel adhesion.

For example, JP-A-2-140220 discloses a rubber-based organic polymer having a crosslinkable methyldimethoxysilyl group and a polyether in the main chain, and a functional group capable of reacting with an epoxy group and a crosslinkable methyl. An adhesive composition in which a silicone compound having a dimethoxysilyl group is added to an epoxy resin is disclosed. This adhesive certainly exhibits good adhesive strength as an adhesive for metals such as aluminum having a high surface energy. This is because the epoxy resin cures spherically in the adhesive by the reaction, and the spherically cured epoxy resin forms a rubber-like cured product by reinforcing the polyether structure of the rubber-based organic polymer. It is believed that there is. However, when this adhesive is used for olefin-based plastics and acrylic-based plastics having a small surface energy, the adhesive strength is insufficient as measured by the present inventors.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve such a problem, and an object of the present invention is to provide a novel adhesive composition having improved adhesive strength. Another object of the present invention is to provide an adhesive composition which can be suitably used for bonding olefin-based plastics and acrylic-based plastics.

[0007]

According to one aspect of the present invention, there is provided a new adhesive comprising: (A) the general formula: -Si (R ¹ ) (OR ² ) ₂ (I) ( In the formula (I), R ¹ and R ² are each a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and may be the same or different.) Rubber-based organic polymer having: 100 parts by weight, (B) In the main chain, a general formula: —R ³ —O— (II) (In the formula (II), R ³ is an alkylene group having 2 to 4 carbon atoms. An epoxy resin having at least one unit represented by the following formula: 1 to 50 parts by weight per 100 parts by weight of (C), (C) an epoxy resin excluding the epoxy resin (B):
(A) 5 to 200 parts by weight per 100 parts by weight, (D) Silanol condensation catalyst: 0.1 to 100 parts by weight of (A)
20 parts by weight, (E) epoxy resin curing agent: ((B) +
(C) 0.1 to 20 parts by weight per 100 parts by weight, and (F) a functional group capable of reacting with an epoxy group and a general formula: —Si (OR ⁴ ) ₃ (III) (in the formula (III), R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.): (A) + (B)
+ (C)) / (F) is 100 / 0.1 to 100/20
(Weight ratio). The adhesive composition, in particular,
It is suitable as an adhesive composition for olefin plastics and acrylic plastics.

In the present invention, “(A) rubber-based organic polymer” refers to a polymer having a polymer having a skeleton with a crosslinkable silyl group represented by the formula (I). (A)
The “polymer having a skeleton” is not particularly limited as long as it contains a structure capable of imparting rubber elasticity to (A). Examples of the polymer constituting the skeleton of (A) include: (A1) polyethers such as polyethylene oxide, polypropylene oxide, and polybutylene oxide; and (A2) dicarboxylic acids such as terephthalic acid, isophthalic acid, and adipic acid, and ethylene glycol. Polyesters obtained by condensation polymerization with glycols such as propylene glycol or ring-opening polymerization of lactones: (A3) Polyolefins such as ethylene-propylene copolymer and polyisobutylene: (A4) Polybutadiene, polyisoprene, isoprene-butadiene (A5) Copolymers of diene such as butadiene or isoprene and a copolymer such as styrene or acrylonitrile: (A6) Hydrogenated polyisoprene , Polybutadiene or Isoprene - butadiene copolymer hydrogenated dienes: (A7) methyl (meth) acrylate, ethyl (meth)
Poly (meth) acrylates obtained by polymerizing (meth) acrylates such as acrylate and butyl (meth) acrylate: (A8) (A) and (A7) (meth) acrylates and vinyl acetate , Copolymers of acrylonitrile, styrene, ethylene and the like: (A9) Polymers obtained by graft-polymerizing a vinyl monomer to the polymer described in any of the above (A1) to (A8): (A10) Examples thereof include polysulfide polymers (in the present specification, acrylic acid and methacrylic acid are collectively referred to as “(meth) acrylic acid”). These polymers can be used alone or in combination, and can be used as a random or block copolymer. In addition, a liquid thing is preferable because it is easy to handle.

Particularly, as the polymer constituting the skeleton of (A),
The above-mentioned (A1) polyethers are preferable, for example, a general formula such as polyethylene oxide and polypropylene oxide: -R ⁵ -O- (IV) (In the formula (IV), R ⁵ is 2-4 carbon atoms. Polyethers having at least one unit represented by a (valent alkylene group) are preferred.

Further, the “crosslinkable silyl group” of (A) is represented by the general formula: —Si (R ¹ ) (OR ² ) ₂ (I) (in the formula (I), R ¹ and R ² are And a hydrocarbon group having 1 to 20 carbon atoms, each of which may have a substituent, and may be the same or different.) And a reactive divalent silyl group. . Specific examples of R ¹ include a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, and a methyl group and an ethyl group are particularly preferable. Further, as R ² , specifically, a methyl group, an ethyl group,
Examples thereof include an alkyl group such as a propyl group, an aryl group such as a phenyl group, and an alkyl group having an ether bond such as a methoxyethyl group and ethoxyethyl. Particularly, an alkyl group is preferable.

The number of the reactive divalent silyl groups in the rubber-based organic polymer (A) is preferably from 1 to 20 per molecule on average, more preferably from 1 to 10 per molecule. It is particularly preferred that there are two to six. Further, the reactive divalent silyl group is preferably located at the molecular terminal of (A) from the viewpoint of excellent reactivity. The number average molecular weight of the rubber organic polymer (A) used in the present invention is from 2,000 to 20,000.
Are preferable, 2000 to 15000 are preferable, and 500
0 to 12000 is particularly preferred. (A) is a liquid,
The viscosity is preferably 500 to 25000 cps at 23 ° C., more preferably 1000 to 20,000 cps, and 3
2,000 to 20,000 cps is particularly preferred.

The above-mentioned rubber-based organic polymer (A) can be produced by a known method (JP-A-61-26872).
No. 0), but a commercially available one may be used. Specifically, Cyril SAT200 (trade name), Cyril SAT030 (trade name), Cyril S manufactured by Kanegafuchi Chemical Industry Co., Ltd.
AT010 (trade name) and Cyril SAX350 (trade name) can be exemplified.

[0013] The term "epoxy resin (B)" in the present invention, the main chain of the general formula: in -R ³ -O- (II) (formula (II), R ³ is alkylene having 2 to 4 carbon atoms Is an epoxy resin having at least one unit represented by the formula: One of the features of the adhesive composition of the present invention is to simultaneously have (B) an epoxy resin having an alkyleneoxy unit in the main chain and (C) a general epoxy resin described later.

As the epoxy resin (B), for example, (B1) glycidyl ether type epoxy resins such as bisphenol A propylene oxide adduct: (B2) glycidyl ether type epoxy resins such as bisphenol A ethylene oxide adduct: (B3) ) Propylene oxide glycidyl ether type epoxy resin: (B4) tetramethylene oxide glycidyl ether type epoxy resin: (B5) hexamethylene diglycidyl ether type epoxy resin: (B6) neopentyl glycol diglycidyl ether type epoxy resin Can be exemplified.

These epoxy resins (B) can be used alone or in combination. Among these epoxy resins (B), those having at least two epoxy groups in the molecule at the terminal of the epoxy resin have high crosslinking reactivity, and have good compatibility after the reaction with the epoxy resin (C) described later. This is preferred for reasons such as Furthermore, the epoxy resin (B) is preferably liquid at room temperature because it is easy to handle. Alternatively, the (B) epoxy resin that is solid at room temperature may be dissolved in the liquid (B) epoxy resin before use.

The epoxy resin (B) can be produced by a known method, but a commercially available epoxy resin may be used. For example, BEO-60E (trade name) manufactured by Shin Nippon Science Co., Ltd., B
PPDGE (trade name) manufactured by TR Co., Ltd. and ED-503 (trade name), ED-506 (trade name) and ED-532 (trade name) manufactured by Asahi Denka Kogyo KK can be preferably used. . The epoxy resin (B) is preferably used in an amount of 1 to 50 parts by weight, particularly preferably 3 to 10 parts by weight, based on the epoxy resin (C) described below (100 parts by weight).

In the present invention, the "(C) epoxy resin" is not particularly limited as long as it is a commonly used epoxy resin except the above-mentioned (B) epoxy resin. Examples of the (C) epoxy resin include: (C1) epichlorohydrin-bisphenol A epoxy resin, epichlorohydrin-bisphenol AD epoxy resin, epichlorohydrin-biphenyl epoxy resin, epichlorohydrin-bisphenol F epoxy resin, glycidyl ether of tetrabromobisphenol A Flame-retardant epoxy resins such as phenylglycidyl ether phosphate: (C2) Epoxy resins obtained by hydrogenating the aromatic ring of the epoxy resin described in (C1): (C3) Novolac epoxy resins: (C4) p -Glycidyl ether oxybenzoate type epoxy resins: (C5) aminophenol-based epoxy resins: (C6) diaminodiphenylmethane-based epoxy resins: (C7) urethane having a urethane bond Modified epoxy resins: (C8) Alicyclic epoxy resins: (C9) Epoxy compounds such as N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate: (C10) poly Glycidyl ethers of glycols such as alkylene glycol diglycidyl ether: (C11) Glycidyl ethers of polyhydric alcohols such as glycerin: (C12) Hydantoin type epoxy resins: (C13) Epoxy compounds of unsaturated polymers such as petroleum resins Class: and the like.

Among these (C) epoxy resins,
Those having at least two epoxy groups in the molecule at the terminal of the epoxy resin are preferable because the cured product has excellent environmental properties such as heat resistance and durability, and has good adhesiveness. Particularly, bisphenol A type epoxy resin is preferable. These (C) epoxy resins can be used alone or in combination. Further, (C)
Epoxy resins are preferred because they are easy to handle at room temperature. In addition, (C) epoxy resin solid at room temperature,
It may be used by dissolving it in a liquid (C) epoxy resin.
(C) The epoxy resin can be produced by a known method, but a commercially available epoxy resin may be used. For example, Epicoat 828 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd. and Epomic R-140 (trade name) manufactured by Mitsui Chemicals, Inc. can be suitably used. The epoxy resin (C) is preferably used in an amount of 5 to 200 parts by weight, based on the rubber-based organic polymer (A) (100 parts by weight).
It is particularly preferred to use 50 parts by weight.

In the present invention, "(D) silanol condensation catalyst" refers to a silanol group formed by hydrolysis of a crosslinkable silyl group described in formulas (I) and (III) and (V) described below. It refers to a catalyst that promotes a condensation reaction between each other, and is not particularly limited as long as it is a known acidic catalyst or basic catalyst.

(D) Silanol condensation catalysts include, for example, (D1) titanates such as tetrabutyl titanate and tetrapropyl titanate: (D2) dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diphthalate, Tin carboxylate such as tin octylate, tin stearate, tin naphthenate: (D3) reaction product of dibutyltin oxide and phthalate, tin compound such as dibutyltin acetylacetonate: (D4) aluminum tris Organic aluminum compounds such as acetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate: (D5) Kirin such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate Compounds: (D6) Lead compounds such as lead octylate: (D7) butylamine, monoethanolamine, monoethanolamine, triethylenetetramine, guanidine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo ( 5,4,0) undecene-7 (DBU)
Amines such as: (D8) Salts of the above-mentioned (D7) amines such as carboxylic acids can be exemplified.

In particular, (D) as a silanol condensation catalyst,
Dibutyltin dilaurate, dibutyltin diacetate, dibutyltin acetylacetonate are preferred. These (D) silanol condensation catalysts can be used alone or in combination. (D) a silanol condensation catalyst,
(A) It is preferable to use 0.1 to 20 parts by weight, based on a rubber-based organic polymer (100 parts by weight),
It is more preferable to use 10 parts by weight, and it is particularly preferable to use 0.8 to 2.0 parts by weight.

In the present invention, the "(E) epoxy resin curing agent" is not particularly limited as long as it is used as a generally used epoxy resin curing agent. For example, (E1) triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, xylylenediamine, phenylenediamine, diaminophenylmethane, diaminodiphenylsulfone, isophoronediamine, 2,4,6-tris ( Amines such as (dimethylaminomethyl) phenol: (E2) tertiary amines: (E3) polyamide resins: (E4) imidazoles: (E5) dicyandiamides: (E6) boron trifluoride compounds: (E7) Carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecinyl succinic anhydride, pyromellitic anhydride, and chlorenic anhydride: (E8) Alcohols: (E9) Nord compounds: (E10) can be exemplified carboxylic acids and the like.

In particular, 2,4,6-tris (dimethylaminomethyl) phenol is preferred. These (E) epoxy resin curing agents can be used alone or in combination. (E) Epoxy resin curing agent is based on ((B) epoxy resin + (C) epoxy resin) (100 parts by weight)
Is preferably used in an amount of 0.1 to 20 parts by weight,
It is more preferable to use 15 parts by weight, and it is particularly preferable to use 5 to 10 parts by weight.

In the present invention, "(F) silicon compound"
Is a functional group capable of reacting with the epoxy group of the epoxy resin (B) and the epoxy group of the epoxy resin (C), and a general formula: —Si (OR ⁴ ) ₃ (III) (in the formula (III), R ⁴ Is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.) And a silicon compound having a crosslinkable silyl group represented by the formula (III): One feature is that the reactive group is a reactive trivalent silyl group.

(F) Examples of the functional group capable of reacting with the epoxy group of the silicon compound include primary, secondary and tertiary amino groups, mercapto groups, epoxy groups and carboxyl groups. Particularly, an amino group is preferable. In the formula (III), R ⁴ may specifically be a hydrocarbon group such as a methyl group, a chloromethyl group, a fluoromethyl group, an ethyl group, a phenyl group, and a vinyl group. And a methyl group is preferred.

As such a silicon compound (F),
For example, (F1) γ-aminopropyltrimethoxysilane, γ-
Aminopropyltriethoxysilane, β-aminoethyltriethoxysilane, γ-aminopropyltri (2-methoxyethoxy) silane, N-β- (aminoethyl)-
γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ
-Amino group-containing silicon compounds such as -aminopropyltrimethoxysilane and γ-anilinopropyltrimethoxysilane: (F2) γ-mercaptopropyltrimethoxysilane,
Silicon compounds containing a mercapto group such as γ-mercaptopropyltriethoxysilane: (F3) γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β
Silicon compounds containing epoxy bonds such as-(3,4-epoxycyclohexyl) ethyltrimethoxysilane: (f4) β-carboxyethyltrimethoxysilane, β
-Carboxyethyl-tri (2-methoxyethoxy) silane, N-β- (N-carboxymethylaminoethyl)
And carboxysilane compounds such as -γ-aminopropyl (trimethoxy) silane.

As such a silicon compound (F),
General formula as exemplified in (F1): R ⁶ -R ⁷ -Si (OR ⁴ ) ₃ (V) [In the formula (V), R ⁶ is an amino group (1 to 4 carbon atoms having an amino group. R ⁷ is a divalent alkylene group having 1 to 4 carbon atoms, R ⁴
Is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. ] Is more preferable.

Particularly, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and N-β- (aminoethyl) -γ-aminopropyltriethoxysilane are preferred. These can be used alone or in combination. These can be produced by a known method, but commercially available ones can be used. In the present invention, (F)
The silicon compound is (A) a rubber-based organic polymer, (B) an epoxy resin and (C) an epoxy resin in a weight ratio,
((A) + (B) + (C)) / (F) is 100 / 0.1
To 100/20, preferably 100 / 0.5 to 100 /
10 is more preferred, and 100/1 to 100/5 is particularly preferred.

Further, it is preferable to add water to the adhesive composition of the present invention. The adhesive composition composed of the above components (A) to (F) requires moisture for curing. This water is usually supplied from the surrounding air surrounding the adhesive composition. Therefore, if the supply of moisture to the adhesive composition is insufficient, a problem may occur in the development of desired adhesive strength. As an example of this, when the thickness of the adhesive layer is large, and when the substrate is used for an adherend with poor moisture permeability, for example, plastics and metals, the inside of the adhesive layer is cured. For example, a case where it takes a long time to do so can be exemplified. Therefore, by adding moisture to the adhesive composition, the adhesive strength can be appropriately controlled, which is preferable.

However, each of the components (A) to (F) used in the adhesive composition of the present invention originally contains moisture. That is, each of the components (A) to (F) may contain water during the production, distribution, and storage processes. This moisture also contributes to the curing of the adhesive composition of the present invention. Therefore, (A) to (F)
The amount of water contained in each component is measured by, for example, the Karl Fischer method, etc., and each component is heated while reducing the pressure to control the amount of water to a desired value, and then water is separately added. Is preferred. In the present invention, (A)
Each component of (F) has been subjected to ordinary production, distribution and storage steps, and the component whose water content satisfies the specifications of each component is used. It is preferable to measure the water content of each of the components (A) to (F) as needed and control the water content to a desired value before use.

The amount of water to be added is usually 0.05 to 1.0 based on the rubber-based organic polymer (A) (100 parts by weight).
Part by weight is preferable, 0.05 to 0.8 part by weight is more preferable, and 0.2 to 0.5 part by weight is particularly preferable. If the amount of water is less than 0.02 parts by weight per 100 parts by weight of the rubber-based organic polymer (A), the curability of the adhesive composition is undesirably reduced. On the other hand, when the amount exceeds 0.8 parts by weight, the storage stability of the adhesive composition decreases, which is not preferable.

The amount of water (the amount of water originally contained in each of the components (A) to (F) + the amount of water to be added) is calculated by temporarily mixing all of the components (A) to (F). Assuming one mixture, in the state before curing, 500 to 1
0000 ppm is preferable, and 1500 to 6000 ppm
Is more preferable, and 3000 to 6000 ppm is particularly preferable. If it is less than 500 ppm, the curability of the adhesive composition is undesirably reduced. On the other hand, if it exceeds 10,000 ppm, the storage stability of the adhesive composition is undesirably reduced.

The adhesive composition of the present invention comprises (A) a rubber-based organic polymer, (B) an epoxy resin, (C) an epoxy resin, (D) a silanol condensation catalyst, (E) an epoxy resin curing agent, and F) In addition to the silicone compound, further, additives such as various fillers, plasticizers, antioxidants, ultraviolet absorbers, lubricants, pigments, foaming agents, viscosity modifiers and the like which are usually added to the adhesive composition are used. Can be added. These additives can be appropriately selected alone or in combination according to the required properties.

There are various modes for using the adhesive composition of the present invention. For example, the adhesive composition of the present invention prepares all the components (A) to (F) to be used, weighs all the components immediately before use, and weighs all the components (A) to (( F) can be used as a mixture. Therefore, the adhesive composition of the present invention can be used as a one-part adhesive composition.

Further, in the adhesive composition of the present invention, all the components (A) to (F) to be used are measured in advance, and a two-pack type or a three-component type is used.
A liquid type adhesive composition can be used by mixing these two or three liquids at a predetermined ratio immediately before use. Accordingly, the adhesive composition of the present invention is provided as a two-part or three-part adhesive composition. In this case, a two-part adhesive composition is preferable, and in particular, (A) a rubber-based organic polymer, (E)
A two-part adhesive composition comprising a composition containing an epoxy resin curing agent and (F) a silicon compound, and a composition containing (B) an epoxy resin, (C) an epoxy resin, and (D) a silanol condensation catalyst. preferable.

Further, in the adhesive composition of the present invention, all the components (A) to (F) to be used are measured in advance to form one combination, and all the components thus measured are used immediately before use. They can be used in combination. Accordingly, (A) a rubber-based organic polymer, (B) an epoxy resin, (C) an epoxy resin, and (D) for constituting the adhesive composition of the present invention.
Provided is a combination of a silanol condensation catalyst, (E) an epoxy resin curing agent and (F) a silicon compound.

The adhesive composition of the present invention can be manufactured by using a method usually used for manufacturing an adhesive composition. For example, the adhesive composition of the present invention can be manufactured by using a mixing pot that can be stirred and can be heated and adjusted in temperature as needed. It is preferable to heat as needed while stirring and mixing the components (A) to (F). When a two-part or three-part adhesive composition is used, components (A) to (F) corresponding to each of the two-part or three-part compositions are mixed, and the same operation as described above is performed. It is preferred to do so.

Further, in the case of producing the adhesive composition of the present invention to which moisture is added, the addition of moisture is carried out while controlling the amount of moisture when producing the adhesive composition. Is preferred. For its production, for example, 80 ° C.
As described above, it is preferable to use a compounding kettle that can be heated to 100 ° C. or more and that can control the temperature, and preferably can be stirred while reducing the pressure. It is preferable to heat and reduce the pressure while stirring and mixing the components (A) to (F) to dehydrate the water in the mixture to a predetermined value or less, and then to add a predetermined amount of water. When a two-part or three-part adhesive composition is used, the composition corresponds to each of the two-part or three-part adhesive compositions (A) to
It is preferable to perform the same operation as described above by mixing the component (F). In addition, a low molecular weight silane compound such as methyltrimethoxysilane can be added as a dehydrating agent.

The adhesive composition of the present invention may be used in a two-part or three-part type.
When a liquid-type adhesive composition is used, the entire amount of the predetermined moisture may be added to any one of the two-component or three-component adhesive composition, or the two-component or Predetermined moisture may be added to two or more compositions constituting the three-part adhesive composition, as appropriate. However, it is preferable to consider the water content and the storage stability of the components constituting the composition.
In particular, the (D) silanol condensation catalyst is usually composed of an organometallic compound, and since the organometallic compound is easily decomposed when the water content is high, the composition containing no (D) silanol condensation catalyst has a higher water content. It is preferable to add water so as to obtain a ratio.

The adhesive composition of the present invention is preferably used particularly for plastics having a low surface energy such as olefin plastics and acrylic plastics. Polyvinyl chloride, ABS resin, fluorine resin, silicone resin, bakelite, polystyrene, polycarbonate, polyacetal, 6-nylon, polyetheretherketone, polyethersulfone, polysulfone, polyamideimide, polyimide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene Plastics such as sulfide and modified polyphenylene oxide, natural rubber, butadiene rubber, styrene
Butadiene rubber, butyl rubber, NBR, silicone rubber,
Rubber such as EPDM, acrylic rubber, fluorine rubber, wood,
It can also be used for hardboard, slate board, calcium silicate board, mortar, concrete, marble, granite and other natural stones and artificial stones.

The adhesive composition of the present invention exhibits excellent adhesive strength even when used for olefin-based plastics and acrylic-based plastics having a small surface polarity. This is considered for the following reasons. It is considered that the adhesive composition of the present invention is substantially a polymer alloy containing (A) a rubber-based organic polymer and (B) an epoxy resin and (C) an epoxy resin as main components. (F) The silicon compound is considered to contribute to compatibilization of (A) and (B) and (C), thereby increasing the strength of the polymer alloy.

When the adhesive composition of the present invention is applied to various adherends, (C) an epoxy resin is mainly coordinated to the polar group on the surface of the adherend, and the olefin-based plastic having a small polarity is used for the polar group. It is considered that (A) a rubber-based organic polymer having a crosslinkable group and (B) an epoxy resin are mainly coordinated. (B)
In the case where is not present, only (A) is coordinated to an olefin-based plastic having a small polarity. With only (A), the coordination force is insufficient and the adhesive force is insufficient.
(B) has the property of coordinating with a low-polarity olefin-based plastic or the like to improve the wettability of its surface.
It is considered that the presence of (B) improves the adhesive strength to olefin-based plastics having a small polarity. In addition, for the reasons described above, the adhesive composition of the present invention is considered to exhibit excellent adhesive strength even for olefin-based plastics and acrylic-based plastics having small surface polarities. The adhesive composition is not subject to any restrictions.

[0043]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, these examples and comparative examples are merely one embodiment of the present invention, and the present invention is not limited by these examples. It is not something to be done.

The components (A) to (F) used for preparing the adhesive compositions of Examples and Comparative Examples are shown below. (A1) and (a2) are (A) rubber-based organic polymers, and (a)
1) is a compound having a dimethoxysilyl group at the terminal and having a molecular weight of 5
000-6000 polypropylene oxide (manufactured by Kaneka Chemical Co., Ltd., Kaneka Cyril SAT30 (trade name)). (A2) is a polypropylene oxide having a dimethoxysilyl group at the terminal and having a molecular weight of 9000 to 10,000 (Kaneka Cyril SAT200 (trade name) manufactured by Kaneka Chemical Co., Ltd.). (B1) and (b)
2) is an epoxy resin (B), and (b1) is an epoxy resin of bisphenol A type having hexaethylene oxide in the main chain (BEO-6, manufactured by Shin Nippon Science Co., Ltd.).
0E (product name)). (B2) is an epoxy resin having polypropylene oxide in the main chain (manufactured by BTR,
PPDGE (product name)).

(C1) is a bisphenol A type epoxy resin (Epicoat 828 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.) of the epoxy resin (C). (D
1) is (D) a silanol condensation catalyst of 3,4,6-trisdiaminomethylphenol (also referred to as "DMP30") (manufactured by BTR, Ancamine K54). (E
1) is a tin compound (SCAT1 (trade name) manufactured by Sankyoki Seisaku Co., Ltd.) as an epoxy resin curing agent (E).
(F1) is (F) a silicon compound of N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane [NH ₂ C ₂ H ₄ NHC ₃ H ₆ Si (OCH ₃ ) ₃ ] (Nippon Unicar ( Co., Ltd., A1120 (trade name)).

Example 1 100 g of dimethoxysilyl-terminated polypropylene oxide having a molecular weight of 5,000 to 6,000 (Kanekasilyl SAT30 (trade name), manufactured by Kaneka Chemical Co., Ltd.) (a1) was stirred at room temperature at room temperature. 50 g of bisphenol A type epoxy resin (Epicoat 828 (trade name), manufactured by Yuka Shell Epoxy Co., Ltd.) (c1) was added. Next, a bisphenol A type epoxy resin having 5 g of hexaethylene oxide in the main chain at room temperature (BEO-60E (trade name) manufactured by Shin Nippon Rika Co., Ltd.) (b1)
, 5 g of 3,4,6-trisdiaminomethylphenol (also referred to as “DMP30”) (manufactured by BTR, Ancamine K54) (d1), and 1.5 g of a tin compound (manufactured by Sankyoki Gosei Co., Ltd.) ), SCAT1 (trade name)) (e
1) 3 g of N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane [NH ₂ C ₂ H ₄ NHC ₃ H ₆ S
i (OCH ₃ ) ₃ ] (A1120, manufactured by Nippon Unicar Co., Ltd.)
(Trade name)) (f1) and 0.5 g of distilled water were added, and the mixture was sufficiently stirred to obtain a desired adhesive composition.

Evaluation of Adhesive Composition Two coated substrates made of polyethylene (300 mm × 300 mm)
mm × 0.2 mm substrate), the adhesive composition of Example 1 was applied with a constant thickness of 0.2 mm using a bar coater, and both were compressed by hand and bonded. After the laminated polyethylene film was sandwiched between plate-like ones having a flat surface, a load was applied thereto at a pressure of 0.2 kg / cm 2 at 20 ° C. for 3 days. The sample obtained after 3 days was cut out to a width of 25 mm and used as an evaluation sample.

With respect to the evaluation sample having a width of 25 mm,
Using a method similar to that of IS K 6854, at 23 ° C.
, A T-type peeling test was performed at a crosshead speed of 50 mm / min, the force at that time was measured, and the result was taken as the adhesive force of the adhesive of Example 1. The results are shown in Table 1 as PE adhesion. An evaluation sample was prepared in the same manner for the coated substrate made of polypropylene, and the T-peel test described above was performed to measure the adhesive strength of the adhesive of Example 1. The result is P
Table 1 shows the P adhesion.

Example 2 An adhesive composition of Example 2 was obtained in the same manner as in Example 1 except that 10 g of (b1) was used instead of 5 g of (b1). . Using the same method as described in Example 1, the adhesive composition of Example 2 was evaluated. The results are shown in Table 1.

Example 3 A method similar to that described in Example 1 was used except that 100 g of (c1) was used instead of 50 g of (c1), and 8 g of (d1) was used instead of 5 g of (d1). Using the method
An adhesive composition of Example 3 was obtained. The adhesive composition of Example 3 was evaluated using the same method as that described in Example 1. The results are shown in Table 1.

Example 4 100 g of (c1) was used instead of 50 g of (c1), 10 g of (b1) was used instead of 5 g of (b1), and 8 g of (d1) was used instead of 5 g of (d1) ), Using the same method as described in Example 1 except that
An adhesive composition of Example 4 was obtained. The adhesive composition of Example 4 was evaluated using the same method as described in Example 1. The results are shown in Table 1.

Example 5 An epoxy resin having 5 g of polypropylene oxide in the main chain instead of 5 g of (b1) (PPD, manufactured by BTR)
An adhesive composition of Example 5 was obtained using the same method as described in Example 1 except that GE (trade name) (b2) was used. The adhesive composition of Example 5 was evaluated using the same method as described in Example 1. The result is
The results are shown in Table 1.

Example 6 An adhesive composition of Example 6 was obtained in the same manner as in Example 1 except that 10 g of (b2) was used instead of 5 g of (b1). . Using the same method as described in Example 1, the adhesive composition of Example 6 was evaluated. The results are shown in Table 1.

Example 7 100 g of (c1) was used instead of 50 g of (c1), and 5 g of (b2) was used instead of 5 g of (b1).
An adhesive composition of Example 7 was obtained by using the same method as that described in Example 1 except that 8 g of (d1) was used instead of 5 g of (d1). The adhesive composition of Example 7 was evaluated using the same method as that described in Example 1. The results are shown in Table 1.

Example 8 100 g of (c1) was used instead of 50 g of (c1), 10 g of (b2) was used instead of 5 g of (b1), and 8 g of (d1) was used instead of 5 g of (d1) ), Using the same method as described in Example 1 except that
An adhesive composition of Example 8 was obtained. The adhesive composition of Example 8 was evaluated using the same method as that described in Example 1. The results are shown in Table 1.

Example 9 Instead of 5 g of (b1), 5 g of (b1) and 5 g of (b1)
An adhesive composition of Example 9 was obtained using the same method as that described in Example 1 except for using 2). Example 1
The adhesive composition of Example 9 was evaluated using the same method as that described in (1). The results are shown in Table 1.

Example 10 100 g of (c1) was used instead of 50 g of (c1), and 10 g of (b1) and 10 g of (b1) were used instead of 5 g of (b1).
g of (b2) and the same method as described in Example 1 except that 8 g of (d1) was used instead of 5 g of (d1). Obtained. Example 10 was performed using the same method as that described in Example 1.
Was evaluated for the adhesive composition. The results are shown in Table 1.

[0058]

[Table 1] a) The unit is g. b) Adhesion to polyethylene, unit is kgf / 2
5 mm. c) Adhesion to polypropylene, unit is kgf /
25 mm.

Comparative Example 1 An adhesive composition of Comparative Example 1 was obtained in the same manner as in Example 1 except that 5 g of (b1) was not used. The adhesive composition of Comparative Example 1 was evaluated using the same method as that described in Example 1. Table 2 shows the results.
It was shown to.

Comparative Example 2 A comparative example was prepared using the same method as described in Example 1 except that 100 g of (c1) was used instead of 50 g of (c1), and 5 g of (b1) was not used. Thus, an adhesive composition of No. 2 was obtained. The adhesive composition of Comparative Example 2 was evaluated using the same method as described in Example 1. The result is
The results are shown in Table 2.

Comparative Example 3 The adhesive composition of Comparative Example 3 was obtained by using the same method as that described in Example 1 except that (b1), (c1) and (d1) were not used at all. . The adhesive composition of Comparative Example 3 was evaluated using the same method as that described in Example 1. The results are shown in Table 2.

COMPARATIVE EXAMPLE 4 (c1) was not used at all and 0.5 g of (d1) was replaced with 0.1 g of (d1).
An adhesive composition of Comparative Example 4 was obtained using the same method as that described in Example 1 except that 5 g of (d1) was used. The adhesive composition of Comparative Example 4 was evaluated using the same method as that described in Example 1. The results are shown in Table 2.

Comparative Example 5 Without using (c1) at all, 10 g of (b1) was substituted for 5 g of (b1).
g of (b1), and using the same method as described in Example 1 except that 1 g of (d1) was used instead of 5 g of (d1), to prepare the adhesive composition of Comparative Example 5. Obtained. The adhesive composition of Comparative Example 5 was evaluated using the same method as described in Example 1. The results are shown in Table 2.

Comparative Example 6 5 g of (b1) was used instead of 5 g of (b1) without using (c1) at all.
Using (b2) of 0.5 g instead of 5 g of (d1)
An adhesive composition of Comparative Example 6 was obtained by using the same method as that described in Example 1 except that (d1) was used. The adhesive composition of Comparative Example 6 was evaluated using the same method as described in Example 1. The results are shown in Table 2.

COMPARATIVE EXAMPLE 7 Without using (c1) at all, 10 g instead of 5 g of (b1)
g of (b2) and the same method as described in Example 1 except that 1 g of (d1) was used instead of 5 g of (d1) to prepare the adhesive composition of Comparative Example 7 Obtained. Using the same method as described in Example 1, the adhesive composition of Comparative Example 7 was evaluated. The results are shown in Table 2.

[0066]

[Table 2] a) The unit is g. b) Adhesion to polyethylene, unit is kgf / 2
5 mm. c) Adhesion to polypropylene, unit is kgf /
25 mm.

Example 11 Instead of (a1), a polypropylene oxide having a dimethoxysilyl group at the terminal and having a molecular weight of 9000 to 10,000 (manufactured by Kaneka Chemical Co., Ltd., Kanekasilyl SAT2)
The adhesive composition of Example 11 was obtained using the same method as that described in Example 1 except that (a (trade name)) (a2) was used. Using the same method as described in Example 1, the adhesive composition of Example 11 was evaluated. The results are shown in Table 3.

Example 12 A method similar to that described in Example 1 was used except that (a2) was used instead of (a1) and 10 g of (b1) was used instead of 5 g of (b1). Thus, an adhesive composition of Example 12 was obtained. The adhesive composition of Example 12 was evaluated using the same method as described in Example 1. The results are shown in Table 3.

Example 13 Substituting (a2) for (a1), 50 g of (c1)
Using 100 g of (c1) instead of 5 g of (d1)
Was used in the same manner as described in Example 1, except that 8 g of (d1) was used instead of (d) to obtain an adhesive composition of Example 13. Using the same method as described in Example 1, the adhesive composition of Example 13 was evaluated. The results are shown in Table 3.

Example 14 Using (a2) instead of (a1), 50 g of (c1)
Was replaced with 100 g of (c1), and 5 g of (b1)
Was replaced by 10 g of (b1) and the same method as described in Example 1 except that 8 g of (d1) was used instead of 5 g of (d1). A composition was obtained. Using the same method as described in Example 1, the adhesive composition of Example 14 was evaluated. The results are shown in Table 3.

Example 15 A method similar to that described in Example 1 was used except that (a2) was used instead of (a1) and 5 g of (b2) was used instead of 5 g of (b1). Thus, an adhesive composition of Example 15 was obtained. The adhesive composition of Example 15 was evaluated using the same method as that described in Example 1. The results are shown in Table 3.

Example 16 A method similar to that described in Example 1 was used except that (a2) was used instead of (a1) and 10 g of (b2) was used instead of 5 g of (b1). Thus, an adhesive composition of Example 16 was obtained. The adhesive composition of Example 16 was evaluated using the same method as that described in Example 1. The results are shown in Table 3.

Example 17 Using (a2) instead of (a1), 50 g of (c1)
Was replaced with 100 g of (c1), and 5 g of (b1)
Was replaced with 5 g of (b2), and instead of 5 g of (d1), 8 g of (d1) was used. A composition was obtained. Using the same method as described in Example 1, the adhesive composition of Example 17 was evaluated. The result is
The results are shown in Table 3.

Example 18 Using (a2) instead of (a1), 50 g of (c1)
Was replaced with 100 g of (c1), and 5 g of (b1)
Was replaced by 10 g of (b2), and instead of 5 g of (d1), 8 g of (d1) was used. A composition was obtained. The adhesive composition of Example 18 was evaluated using the same method as described in Example 1. The results are shown in Table 3.

Example 19 The procedure described in Example 1 was repeated except that (a2) was used instead of (a1) and 5 g (b1) and 5 g (b2) were used instead of 5 g (b1). The adhesive composition of Example 19 was obtained using the same method. The adhesive composition of Example 19 was evaluated using the same method as described in Example 1. The results are shown in Table 3.

Example 20 Using (a2) instead of (a1), 50 g of (c1)
Was replaced with 100 g of (c1), and 5 g of (b1)
Was replaced by 10 g of (b1) and 10 g of (b2), and instead of 5 g of (d1), 8 g of (d1) was used.
An adhesive composition of Example 20 was obtained. The adhesive composition of Example 20 was evaluated using the same method as described in Example 1. The results are shown in Table 3.

[0077]

[Table 3] a) The unit is g. b) Adhesion to polyethylene, unit is kgf / 2
5 mm. c) Adhesion to polypropylene, unit is kgf /
25 mm.

Comparative Example 8 The adhesive composition of Comparative Example 8 was prepared in the same manner as in Example 1 except that (a2) was used in place of (a1) and (b1) was not used at all. I got something. The adhesive composition of Comparative Example 8 was evaluated using the same method as that described in Example 1. The results are shown in Table 4.

Comparative Example 9 Using (a2) instead of (a1), 50 g of (c1)
Was replaced with 100 g of (c1), and the same method as described in Example 1 was used, except that (b1) was not used at all, to obtain an adhesive composition of Comparative Example 9. Example 1
The adhesive composition of Comparative Example 9 was evaluated using the same method as that described in Comparative Example 9. The results are shown in Table 4.

Comparative Example 10 (a2) was used instead of (a1), and (c1), (b)
An adhesive composition of Comparative Example 10 was obtained using the same method as that described in Example 1 except that 1) and (d1) were not used at all. The adhesive composition of Comparative Example 10 was evaluated using the same method as described in Example 1. The results are shown in Table 4.

Comparative Example 11 Example 1 was repeated except that (a2) was used in place of (a1), (c1) was not used at all, and 0.5 g of (d1) was used instead of 5 g of (d1). The adhesive composition of Comparative Example 11 was obtained using the same method as described. Using the same method as described in Example 1, the adhesive composition of Comparative Example 11 was evaluated. The results are shown in Table 4.

Comparative Example 12 (a2) was used instead of (a1), (c1) was not used at all, 10 g of (b2) was used instead of 5 g of (b1), and 5 g of (d1) was used instead of 5 g of (d1) Using a method similar to that described in Example 1 except that 1 g of (d1) was used,
An adhesive composition of Comparative Example 12 was obtained. Using the same method as described in Example 1, the adhesive composition of Comparative Example 12 was evaluated. The results are shown in Table 4.

Comparative Example 13 (a2) was used instead of (a1), (c1) was not used at all, 5 g of (b2) was used instead of 5 g of (b1), and 5 g of (d1) was used instead of 5 g of (d1) An adhesive composition of Comparative Example 13 was obtained by using the same method as that described in Example 1 except that 0.5 g of (d1) was used. The adhesive composition of Comparative Example 13 was evaluated using the same method as that described in Example 1. The results are shown in Table 4.

Comparative Example 14 (a2) was used instead of (a1), (c1) was not used at all, 10 g of (b2) was used instead of 5 g of (b1), and 5 g of (d1) was used instead of 5 g of (d1) Using a method similar to that described in Example 1 except that 1 g of (d1) was used,
The adhesive composition of Comparative Example 14 was obtained. The adhesive composition of Comparative Example 14 was evaluated using the same method as that described in Example 1. The results are shown in Table 4.

[0085]

[Table 4] a) The unit is g. b) Adhesion to polyethylene, unit is kgf / 2
5 mm. c) Adhesion to polypropylene, unit is kgf /
25 mm.

[0086]

According to the present invention, a novel adhesive composition having improved adhesive strength can be provided. This adhesive composition is particularly suitable as an adhesive for olefin and acrylic plastics. Can be used.

Continued on the front page F term (reference) 4J040 CA031 CA032 DA061 DA062 DA121 DA122 DA131 DA132 DA151 DA152 DB041 DB042 DE021 DE022 DF041 DF042 DF051 DF052 DF081 DF082 DL001 DL002 EC021 EC022 EC061 EC062 EC201 EC102 EC101 EC102 EC201 EC262 EC341 EC342 EC401 EC402 ED011 ED012 ED04 ED041 ED051 ED052 ED161 ED162 EE001 EE002 EE051 EE052 EG002 EJ011 EJ012 GA31 HA326 HB07 HB22 HB23 HB35 HC01 HC02 HC06 HC09 HC16 HC24 HD42 HD13 HD13 HD35 HD13 HD35 HD13 HD35

Claims (10)

[Claims] (A) General formula: —Si (R ¹ ) (OR ² ) ₂ (I) (In the formula (I), R ¹ and R ² each have 1 carbon atoms which may have a substituent. a 20 hydrocarbon group, rubber-based organic polymer having a crosslinkable group represented by may be the same or different):. 100 parts by weight, in the main chain (B), the general formula: -R ³ —O— (II) (In the formula (II), R ³ is an alkylene group having 2 to 4 carbon atoms.) An epoxy resin having at least one unit represented by the formula: 1 to 100 parts by weight of (C) (C) epoxy resin except epoxy resin (B): (A)
5 to 200 parts by weight per 100 parts by weight, (D) silanol condensation catalyst: 0.1 to 20 parts by weight per 100 parts by weight of (A), (E) epoxy resin curing agent: ((B) + ( C)) 100
0.1 to 20 parts by weight per part by weight, and (F) a functional group capable of reacting with an epoxy group and a general formula: —Si (OR ⁴ ) ₃ (III) (In the formula (III), R ⁴ is a substituted group. A silicon compound having a crosslinkable group represented by the formula: ((A) + (B)
+ (C)) / (F) is 100 / 0.1 to 100/20
An adhesive composition composed of an amount of a ratio (weight ratio). (A) The main chain of the rubber-based organic polymer is represented by the following general formula: -R ⁵ -O- (IV) (In the formula (IV), R ⁵ is a divalent group having 2 to 4 carbon atoms. At least one unit represented by the formula:
The adhesive composition according to claim 1, wherein the adhesive composition has one. 3. The rubber-based organic polymer (A) has a number average molecular weight of 2,000 to 20,000 and a viscosity of 500 to 25,000 c.
The adhesive composition according to claim 1, which has a ps (23 ° C.). 4. The adhesive composition according to claim 1, wherein the epoxy resin (C) is a bisphenol A type. (F) The silicon compound has a general formula: R ⁶ -R ⁷ -Si (OR ⁴ ) ₃ (V) [In the formula (V), R ⁶ is an amino group (C 1 having an amino group and having 1 carbon atom. And R ⁷ may be substituted with an alkyl group having 1 to 4 carbon atoms.), R ⁷ is a divalent alkylene group having 1 to 4 carbon atoms, R ⁴
Is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The adhesive composition according to any one of claims 1 to 4, wherein 6. The adhesive composition according to claim 1, further comprising water. 7. The adhesive composition according to claim 6, wherein the amount of water added is 0.05 to 1.0 part by weight based on 100 parts by weight of (A). 8. The adhesive composition according to claim 1, which is for bonding a polyolefin plastic and an acrylic plastic. 9. The adhesive composition according to claim 1, wherein the composition comprises (A) a rubber organic polymer, (E) an epoxy resin curing agent, and (F) a silicon compound. A two-part adhesive composition comprising a composition containing B) an epoxy resin, (C) an epoxy resin, and (D) a silanol condensation catalyst. 10. A rubber-based organic polymer (A) for constituting the adhesive composition according to claim 1.
(B) epoxy resin, (C) epoxy resin, (D) silanol condensation catalyst, (E) epoxy resin curing agent, and (F)
Combination of silicon compounds.