JP2000191876A - Silicone aqueous emulsion type resin composition, aqueous emulsion type adhesive and aqueous putty - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone aqueous emulsion type resin composition exerting a wide range of adhesion, a high adhesion strength and a long-term shelf stability using a water dispersion of a polymer without blending any volatile organic compound(VOC) such as an organic solvent and/or plasticizer, and an aqueous emulsion type adhesive and an aqueous putty using this. SOLUTION: A silicone aqueous emulsion type resin composition contains a water dispersion of a polymer, prepared by emulsion copolymerizing a non- silicone, polymerizable unsaturated monomer in the presence of a polymerizable unsaturated monomer having an alkoxysilyl group, an adhesion-imparting resin having an acid number of from 100 to 300 and a compound having both (a) an epoxy group or glycidyl group and (b) an alkoxysilyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone-based aqueous emulsion-type resin composition having a wide range of adhesive properties and excellent adhesive strength and having long-term storage stability, and an aqueous emulsion-type resin composition using the same. It relates to an adhesive and an aqueous putty.

[0002]

2. Description of the Related Art An organic solvent type adhesive obtained by diluting an organic polymer having relatively high adhesiveness such as an acrylic polymer in an organic solvent and an aqueous emulsion type adhesive obtained by dispersing the same in water are far more adhesive. It is known that the adhesive strength differs from the adhesive symmetry range. In general, aqueous emulsion adhesives have the advantages of significantly less danger, harm, and environmental impact than organic solvent-based adhesives, but they have basic adhesive functions such as adhesiveness and adhesive strength. Inferiority is a drawback. As a means of this improvement, it is common to mix a small amount of an organic solvent and / or a plasticizer with various aqueous emulsion type adhesives. In addition, a technical means has been proposed in which various adhesion improvers such as a tackifier resin are blended with an aqueous emulsion adhesive which requires a wide range of adhesion. However, when an adhesiveness improving component such as a tackifying resin is blended, it is necessary to dissolve them in an organic solvent and / or a plasticizer, and eventually, in an aqueous emulsion type adhesive requiring a wide range of adhesiveness, Without any direct or indirect organic solvent and / or plasticizer,
No technical means have been developed to raise the bond strength to a practical level. Furthermore, a practical all-purpose aqueous emulsion type adhesive that can adhere to a wide range of adherends such as plastic, rubber, metal, concrete, stone, wood, etc., using an aqueous emulsion adhesive using a general organic polymer. At present, adhesives are not commercially available without the inclusion of organic solvents and / or plasticizers. Heretofore, the inclusion of a small amount of about several percent of an organic solvent and / or a plasticizer in an aqueous emulsion type adhesive has hardly been regarded as a problem. Conventionally, on the premise of containing a small amount of an organic solvent and / or a plasticizer, the purpose is to develop an aqueous emulsion type adhesive having adhesiveness and adhesive strength close to that of an organic solvent type adhesive. there were. However, in recent years, chemical hypersensitivity typified by new diseases has been caused by volatile organic substances (VOC) such as organic solvents or plasticizers. Therefore, a technique for thoroughly removing volatile organic substances (VOC) such as an organic solvent and / or a plasticizer from the composition of an aqueous emulsion type adhesive has become an important issue today. Unfortunately, no practical universal aqueous emulsion adhesive containing no VOC has been found in the market.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a wide range of adhesion and excellent properties by using a polymer aqueous dispersion without using any volatile organic substance (VOC) such as an organic solvent and / or a plasticizer. An object of the present invention is to provide a silicone-based aqueous emulsion-type resin composition having adhesive strength and long-term storage stability, and an aqueous emulsion-type adhesive and an aqueous putty using the same.

[0004]

Means for Solving the Problems The present inventors have developed a technique for achieving the above-mentioned object in a technique of combining an organic polymer, mainly an acrylic polymer, a tackifying resin, and various adhesion improving agents. I have been doing research for many years. In the course of the research, a polymer aqueous dispersion obtained by emulsion copolymerization of an unsaturated monomer having an alkoxysilyl group and a non-silicone unsaturated monomer, a specific tackifying resin, and a specific alkoxysilyl group-containing compound were used. It has been discovered that the combined silicone-based aqueous emulsion-type resin composition has not only the long-term storage stability required for general-purpose products in the market, but also a wide range of adhesiveness and excellent adhesive strength. Furthermore, it was also confirmed that the effect of the present invention could not be obtained when any of the constituents was different. The aqueous emulsion type adhesive and the aqueous putty using the silicone-based aqueous emulsion type resin composition exhibit excellent adhesiveness and adhesive strength to a wide range of adherends without containing VOC. Upon confirmation, the present invention has been completed.

Hereinafter, the present invention will be described specifically.

That is, the present invention relates to a polymer aqueous dispersion obtained by emulsion-copolymerizing a non-silicone polymerizable unsaturated monomer in the presence of a polymerizable unsaturated monomer having an alkoxysilyl group, and an acid value of 100. A tackifying resin of ~ 300,
And (a) an epoxy group or glycidyl group, and (b) a compound having both (a) and (b) alkoxysilyl groups. Aqueous emulsion type adhesive and aqueous putty. The mixing ratio of each component of the silicone-based aqueous emulsion-type resin composition is such that the tackifying resin is 1 to 50 parts by weight, preferably 5 to 40 parts by weight per 100 parts by weight of the polymer in the polymer aqueous dispersion.
Parts by weight, particularly preferably 10 to 20 parts by weight, and the compound is present in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 10 parts by weight.
To 5 parts by weight, particularly preferably 0.1 to 1 part by weight.

When the amount of the tackifying resin is less than 1%, the adhesive strength of the resin composition film to various substrates becomes weak, and when the amount is more than 50%, the film becomes brittle, which is not preferable. If the amount of the compound is less than 0.01 part by weight, the water-resistant adhesive strength of the film becomes weak, and if it is more than 10 parts by weight, the film becomes weak and the cost becomes high, which is also not preferable. In addition, as necessary, fillers, thickeners, coloring agents (pigments, dyes), preservatives, wetting agents,
Various performances can be added by adding an acid absorbent, an antioxidant, a coupling agent and the like.

[0008] The aqueous polymer dispersion is a mixture of a polymerizable unsaturated monomer having an alkoxysilyl group and a non-silicone polymerizable unsaturated monomer in the presence of an emulsifier. It is a polymer aqueous dispersion obtained by emulsion polymerization using an initiator such as an alkali. There is also a method in which a mercapto compound having an alkoxysilyl group such as trimethoxypropylmercaptosilane is used as a chain transfer agent instead of the polymerizable unsaturated monomer having an alkoxysilyl group. Of course, both a polymerizable unsaturated monomer having an alkoxysilyl group and a mercapto compound may be used. Examples of the unsaturated monomer having an alkoxysilyl group include trimethoxyacryloylsilane, trimethoxymethacryloylsilane, vinyltriethoxysilane, γ
-Methacryloxypropyltrimethoxysilane and the like are used.

As the non-silicone polymerizable unsaturated monomer, alkyl acrylates having an alkyl group having 1 to 8 carbon atoms (eg, methyl acrylate,
Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), alkyl methacrylates having an alkyl group of 1 to 8 carbon atoms (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, etc., fatty acid vinyls having 1 to 10 carbon atoms in fatty acids (eg, vinyl acetate, vinyl propionate, vinyl versatate, etc.), styrene, diene monomers (eg, chloroprene, butadiene, isoprene, etc.) , Vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, maleic acid monoester, maleic acid diester, and the like.

The tackifier resin has an acid value of 1
A maleic acid-added compound of rosin acid (maleic acid-modified rosin), a copolymer of styrene and maleic acid, a maleic acid resin, or the like is used. Here, the acid value is a value in milligrams of potassium hydroxide required for neutralizing the acid contained in 1 g of the resin. If the acid value of the tackifying resin is not more than 100, it is not easily dissolved in water. On the other hand, if the acid value is not less than 300, the water-resistant adhesiveness is undesirably weak. (A) above
And (b) compounds having both groups (epoxysilane) include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, β
-(3,4 epoxycyclohexyl) ethyltrimethoxysilane and the like are used.

Next, the silicone-based aqueous emulsion-type resin composition of the present invention exhibits excellent adhesion and adhesive strength to a wide range of adherends and has long-term storage stability. It will be described. Although the theoretical elucidation of the cause has not been sufficiently made, the following reasons are considered for the time being.

The aqueous polymer dispersion is obtained by emulsion copolymerization of an unsaturated monomer having an alkoxysilyl group and another non-silicone unsaturated monomer, and the alkoxysilyl group is hydrolyzed. Therefore, at the end of the polymerization, silanolation or polysiloxane bond is partially formed.
The tackifying resin is present in the aqueous phase as a polymer aqueous solution or microsol. And (a) and (b) above
The alkoxysilyl group of the compound having both groups is partially silanolized or forms a polysiloxane bond with silanol similarly to the above-mentioned polymer, while the epoxy group is also present in the aqueous phase. Furthermore, this above
The compound having both the (a) and (b) groups is not only hydrolyzed and self-crosslinked, but also interacts with the silanol present in the polymer to form a polysiloxane, because the compound is mixed with the polymer aqueous dispersion once prepared. It is considered that a bond is also formed. In general, a polymer emulsion having such a cross-linking property tends to cause thickening or gelation over time, but the present invention is excellent in long-term storage stability.

[0013] Then, in the silicone-based aqueous emulsion-type resin composition of the present invention having the above-mentioned complicated crosslinked structure, the polymer (backbone polymer) has a silanolation or a siloxane bond, and is present in the aqueous phase with the polymer. In addition, there is an interaction with the above-mentioned tackifying resin, and there is silanolation or siloxane bond (self-crosslinking and polymer crosslinking) of the compound having both (a) and (b) groups. There are residual epoxy groups. Therefore, it is considered that the cohesive strength of the silicone-based aqueous emulsion-type resin composition of the present invention is improved as compared with a simple blend because of its complicated crosslinked structure, and the presence of an epoxy group and a silanol group improves the interfacial function. It is a factor. Such complex cross-linked structures and interactions are responsible for providing excellent bonding functions (adhesion and bonding strength) to a wide range of adherends such as plastic, rubber, metal, concrete, stone, and wood. It is inferred.

On the other hand, the compound having both the (a) and (b) groups has volatility by nature, but has the advantage of no longer being a VOC because it exists in the aqueous phase and is polymerized for the above-mentioned reason. In addition, it can be said that if any one of the above-mentioned components is different, the interaction is lost and the effect of the present invention is not obtained. Subsequently, in order to process the silicone-based aqueous emulsion-type resin composition of the present invention into an aqueous emulsion-type adhesive and an aqueous putty, the tackifier resin is mixed with the polymer aqueous dispersion obtained by emulsion polymerization, Next, an appropriate amount of a thickener (water-soluble polymer) is added to make the mixture uniform, and further a filler such as calcium carbonate is mixed. Thereafter, the above compound and a usual additive are added, followed by defoaming under reduced pressure.

The aqueous emulsion type adhesive and the aqueous putty thus obtained are packed in a tube or the like, extruded from a nozzle and applied in a bead form, or brushed, roll-coated or sprayed on one side of the adherend. Alternatively, they may be applied to both sides and bonded together immediately, or may be bonded together after taking an open time. Next, the silicone-based aqueous emulsion-type composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0016]

EXAMPLES Example 1 A flask equipped with a condenser and a stirrer was immersed in a water bath capable of controlling the temperature, in which 38 parts by weight of water, an anionic surfactant (sodium alkyldiphenyl ether disulfonate, active ingredient = 30) were used.
%) And 2 parts by weight of a nonionic surfactant (polyethylene nonyl phenyl ether, HLB = 18.0) are charged and dissolved. After this, the temperature in the flask is raised to 75 ° C.
And a mixture of 31 parts by weight of butyl acrylate, 26 parts by weight of methyl methacrylate, 1 part by weight of acrylic acid, and 0.1 part by weight of γ-methacryloxypropyltrimethoxysilane was added to 10% of ammonium persulfate. Emulsion polymerization was performed by dropwise addition over 3 hours together with 1.1 parts by weight of the aqueous solution to obtain emulsion A. This emulsion has a non-volatile content (solid content) of 59.8% and a P
H had a physical property of 3.8 and a viscosity of 1250 Pa · s.

Next, to 100 parts by weight of the emulsion A, a mixture of 10 parts by weight of maleic acid-modified rosin having an acid value of 200, 15 parts by weight of water, and 4 parts by weight of aqueous ammonia (25% aqueous solution) was added and stirred. 100 parts by weight of calcium (heavy powder, average particle size: about 1 μm) and 0.1 part by weight of γ-glycidoxypropyltrimethoxysilane are sequentially added, mixed and stirred, and a silicone-based aqueous emulsion adhesive composition is added. A was obtained. The solid content of the adhesive composition is
74.2% by weight and PH was 7.8. Then, the adhesive composition A is applied to a slate plate (base) using a C-1 type comb iron, and a wood, a porcelain tile, styrofoam, and an aluminum adherend are adhered thereto, and JIS A
Cured under standard conditions (environmental conditions) of 1611, then adhered a steel attachment (4 cm x 4 cm) to each adherend with a quick mender (epoxy resin-based fast-curing adhesive). [Unit: N / mm
² ] and the results shown in Table 1 below were obtained.

Example 2 In Example 1, 17 parts by weight of butyl acrylate and 40 parts by weight of vinyl acetate were used instead of 31 parts by weight of butyl acrylate and 26 parts by weight of methyl methacrylate. Others were performed exactly like Example 1, and the result shown in Table 1 below was obtained. (Example-3) The procedure of Example-1 was repeated, except that a styrene-maleic acid resin having an acid value of 200 was used instead of the maleic acid-modified rosin having an acid value of 200. Were obtained.

Next, for comparison, one of the above-mentioned components (1) to (4) of the present invention was subjected to a tensile adhesive strength test in the same manner as in Example 1, except that one of the above components was not replaced or used. The results are also shown in Table 1 below as Comparative Examples 1 to 3. (Comparative Example 1) The procedure of Example 1 was repeated, except that γ-methacryloxypropyltrimethoxysilane was not added.

(Comparative Example 2) In Example 1, instead of a mixture of 10 parts by weight of maleic acid-modified rosin having an acid value of 200/15 parts by weight of water / 4 parts by weight of aqueous ammonia (25% aqueous solution), a softening point was used. Except that 29 parts by weight of a rosin ester resin emulsion (solid content = 50%) at 120 ° C. was used, the procedure was exactly the same as in Example-1. (Comparative Example 3) The procedure of Example 1 was repeated, except that γ-glycidoxypropyltrimethoxysilane was not added.

[0021]

[Table 1]

[0022]

The silicone-based aqueous emulsion-type resin composition of the present invention is prepared by using a specific polymer aqueous dispersion and a volatile organic substance (VOC) such as an organic solvent and / or a plasticizer.
Because it is not blended at all, it does not harm the environment and has no danger, and also exhibits excellent adhesion to a wide range of materials including wood, paper, concrete, ceramics, stone, metal, and plastic, In addition, since it has long-term storage stability, it can be suitably used as a VOC-free universal aqueous emulsion adhesive, an aqueous putty, and the like.

Continued on the front page F-term (reference) 4J002 AF022 BG041 BG051 BG061 BG071 BH012 BQ001 CP171 EX066 FD146 FD342 GJ00 GJ01 HA07 4J038 BA232 CA021 CC021 CD021 CD081 CF011 CG021 CG071 CG141 CH041 PC04 NA07 PC04 CA061 CA111 CA161 DB041 DB042 DC031 DC071 DE011 DE021 DF011 DF041 DF051 DG011 DJ031 EC282 EK111 GA29 GA31 HD35 JA03 KA16 KA26 LA05 LA06

Claims (7)

[Claims] 1. A polymer aqueous dispersion obtained by emulsion-copolymerizing a non-silicone polymerizable unsaturated monomer in the presence of a polymerizable unsaturated monomer having an alkoxysilyl group, and an acid value of 100.
And (a) an epoxy group or a glycidyl group and (b) an alkoxysilyl group.
And (b) a compound having both groups. 2. The non-silicone polymerizable unsaturated monomer constituting the polymer of the polymer aqueous dispersion is an alkyl acrylate, an alkyl methacrylate,
The silicone-based aqueous emulsion-type resin composition according to claim 1, comprising at least one of a fatty acid vinyl and styrene, wherein the content of the silicone-based aqueous emulsion-type resin composition is 40 to 70 parts by weight based on 100 parts by weight of the polymer. 3. The tackifying resin having an acid value of 100 to 300 is a maleic acid addition compound of rosin acid or a copolymer of styrene and maleic acid. The silicone-based aqueous emulsion-type resin composition according to item 1. 4. The compound having (a) an epoxy group or a glycidyl group and (b) a compound having both (a) and (b) groups of an alkoxysilyl group is an epoxysilane coupling agent. The silicone-based aqueous emulsion-type resin composition according to any one of claims 1 to 3. 5. The polymer aqueous dispersion of the polymer
1 to 50 parts by weight of the tackifying resin and the compound 0.0 having both the groups (a) and (b) 0.0
The silicone-based aqueous emulsion-type resin composition according to any one of claims 1 to 4, wherein 1 to 10 parts by weight is blended. 6. An aqueous emulsion-type adhesive comprising the silicone-based aqueous emulsion-type resin composition according to any one of claims 1 to 5. 7. An aqueous putty using the silicone-based aqueous emulsion-type resin composition according to any one of claims 1 to 5.