JPH02272080A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in adhesivity to adherends and capable of imparting the coating applied thereon with high wear resistance by incorporating a cyclic dimethylsiloxane with an acidic substance, halogenating agent and a specific diaminosilicone. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100 pts.wt. of a cyclic dimethylsiloxane such as cyclic tri(or tetra)siloxane with (B) pref. 0.01-1 pt.wt. of an acidic substance such as sulfuric acid, trifluoroacetic acid, iron chloride or acid clay, (C) pref. 0.002-20 pts.wt. of a halogenating agent (pref. alkylhypohalide or hypohalogen acid salt) and (D) pref. 0.01-30 pts.wt. of a diaminosilicone of the formula (l1 and l2 are each 2-6; amine equivalent is 300-2500).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adhesive composition for adhering rubber products, synthetic resin products, etc.

[Prior art] Generally, natural rubber (NR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (8R), isobutylene-isoprene copolymer rubber (ITR), chloroprene rubber (CR), acrylonitrile-butadiene copolymer Synthetic rubbers such as rubber (NBR), inbrene rubber <IR,), ethylene-propylene-diene copolymer rubber (EPDM), ethylene-propylene copolymer rubber (EPM), fibers such as cotton and rayon, and acrylonitrile-butadiene-styrene. Polymer (ABS), polystyrene (PS)
Synthetic resins such as these are used as base materials for double-sided tapes.

For example, double-sided tape used to attach side protection moldings (hereinafter referred to as moldings) to the side of an automobile body is made by applying an adhesive made of synthetic resin to both sides of the base material, such as rubber or synthetic resin. It is configured.

In addition, rubber such as EPDM, EPM, NR, 5BR2CR, polyethylene (PE), polypropylene (PP)
In order to improve the abrasion resistance on the surface of resin such as ethylene-vinyl acetate copolymer (EVA), polyurethane is applied.

[Problems to be Solved by the Invention] However, wax remover is used to wipe off wax applied to a car during a car wash, or wax remover is accidentally spilled when refilling fuel such as gasoline.
When these solvents such as wax remover gasoline adhere to the side edges of the double-sided tape, there is a problem in that the base material swells or dissolves. Furthermore, is the solvent attached to the side edges of the double-sided tape between the double-sided tape and the molding or between the double-sided tape and the car body? In the case of ti3, there was a problem that the bonding area between the two became small and the tensile shear strength and peel strength decreased.

For example, a coated steel plate and a vinyl chloride resin plate bonded using the double-sided tape are immersed in gasoline, wax remover, etc. at room temperature (23°C) for 1 hour, and then the bonded area and tensile shear strength are measured. As a result, the adhesive area was 1
At the same time, the tensile shear strength decreased from 8.8 kg/crA to 1.5 kg/cal.

Further, there was a problem in that the adhesiveness of polyurethane applied to improve the abrasion resistance on the surface of rubber or resin was insufficient.

An object of the present invention is to provide an adhesive composition that has good adhesion to adherends and provides excellent abrasion resistance to the paint applied thereon.

[Means for Solving the Problems 1] In order to achieve the above object, the present invention employs a method consisting of a cyclic dimethylsiloxane, an acidic substance, a halogenating agent, and a diamino silicone having the following structure.

CI(3CH3 CH3CH3 (CH2) 4 t NH(CH2) 12 N
H2 However, each of 121.122 is 2 to 6, and the amine equivalent is 300 to 25,000.

[Detailed explanation of means] Cyclic dimethylsiloxane is a siloxane bond (St-
0-3i), for example, cyclic dimethyltrisiloxane, cyclic dimethyltetrasiloxane, etc. can be used.

As the acidic substance, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and boric acid, organic acids such as trifluoroacetic acid, metal salts such as iron chloride, and acidic substances such as acid clay can be used.

The blending ratio of the acidic substance is 1 part cyclic dimethylsiloxane
00 parts by weight, a range of 0.01 to 1 part by weight is suitable. If the blending ratio of this acidic substance is less than 0.01 parts by weight, the effects of cyclic dimethylsiloxane such as interlocking properties and sealing properties will not be fully exhibited, and if it exceeds 1 part by weight, the acidic substances will become impurities. Performance tends to deteriorate.

Examples of the halogenating agent include t-butylhypochloride (t-BHC) as the alkylhypohalide.
, sodium hypochlorite as hypohalite,
Potassium hypochlorite, compounds with -CONX- bonds (x is a halogen atom) in the molecule include N-bromosuccinimide (NBSI), trichlorisocyanuric acid (TCIA),
), isocyanuric dichloride M (DiCIA), antimony pentafluoride, a mixed solution consisting of sulfur fluoride and bromine, etc., among which are alkyl hypohalides, hypohalites or - in the molecule. Compounds having a CONX-bond are preferred.

The mixing ratio of this halogenating agent is preferably in the range of 0.002 to 20 parts by weight based on 100 parts by weight of the cyclic dimethylsiloxane. This blending ratio is 0. If it is less than OO2, the degree of halogenation is small, so that the improvement in adhesive strength is small, and if it exceeds 20 parts by weight, the stability of the adhesive composition tends to deteriorate.

Diaminosilicone is a compound represented by the following formula.

ct-t3 CH3 CH3CH3 However, 61. ! 2 is each 2 to 6, the amine equivalent is 300 to
It is 25,000.

The above n and m are determined based on this amine equivalent. If these (11, 62) are too small, diamino silicone will not function as a hardening agent, etc., and if it is too large, mold release properties similar to those of silicone oil will appear, which is undesirable. The kinematic viscosity is preferably in the range of 100 to 100,000 centistokes (Cst).

The blending ratio of this diamino silicone is in the range of 0.01 to 30 parts by weight per 100 parts by weight of cyclic dimethylsiloxane. If it is less than 0.01 parts by weight, it will not be possible to impart i+ abrasion properties and adhesiveness will also decrease, and if it exceeds 30 parts by weight, these effects will not improve.

[Operation] By adopting the above means, the halogenating agent in the adhesive composition halogenates the adhesive composition itself and halogenates the adherend, thereby improving the adhesiveness between the adhesive composition and the adherend. In addition, when the adhesive composition is used as a primer and a urethane-based paint is applied thereon, the diamino silicone reacts with the polyurethane and improves the adhesion between the urethane-based paint and the coating film. It is estimated that it exhibits excellent wear resistance. Further, the film of the adhesive composition exhibits functions such as 11 water resistance, sealing property, and solvent resistance mainly due to the cyclic dimethylsiloxane containing an acidic substance.

[Examples 1 to 12 and Comparative Example 1.2] Examples that embody the adhesive composition of the present invention will be described below.

(1) Brimer (adhesive composition) Table below for 100 parts of cyclic dimethyltrisiloxane -
A brimer was prepared by mixing predetermined amounts of the acidic substance shown in 1, a halogenating agent, and diamino silicone.

(2) Coating composition Polyol and polyisocyanate (O
H/NC0=1/2 to 1/10 (molar ratio)] and reacted in dry nitrogen at 80° C. for 3 hours. A coating composition was prepared by adding silicone oil and fluorine resin shown in Table 2 to the obtained reaction solution.

(3) Preparation of test piece and evaluation of abrasion resistance Vulcanized rubber (EPDM) was used as a base material, and after coating the primer to a thickness of about 10 μm on the surface and drying, the coating composition was applied. was applied to a thickness of about 50 μm to prepare a test piece. The wear resistance of this test piece was evaluated using the following test method. The results are shown in Table-3.

Test machine: Tipper type rotary abrasor (manufactured by Toyo Seiki Seisakusho Co., Ltd.) Test conditions: Wear wheel, H-22, Load: 1 kg Wear rotation speed: 5 Qrpm Sample size: 100 cranes x 10011 Number of wear: 1000 times Table -1 The abbreviations in Table-1 represent the following meanings.

t-BHC: t,-butylhypochloride NBSI
:N-bromosuccinimide TCIA:) Lichloroisocyanuric acid (1); specific gravity (25°C) 8,913, refractive index (25°C)
)1゜421, amine equivalent (meq/mg) 360
Diamino silicone (2): specific gravity (25°C) 0.98, refractive index (25°C)
L410, amine equivalent <meq/mg) 830 diamine, silicone (3); specific gravity (25'c) 0.96, refractive index (25°C
)1゜403, amine equivalent (meq/mg) 2250
0 diamino silicone (4): specific gravity (25°C) 0.97, refractive index (25°C)
l.

404, amine equivalent (meq/mg) 7600 diamino silicone (5): specific gravity (25°C) 0.98, refractive index (25°C) 1
407, diamino silicone (6) with amine equivalent (meq/mg) 2000; specific gravity (25°C) 0.9g, refractive index (25°C)
].

Diaminosilicone (7) with 40 mA, amine equivalent (meq/mg) X900: ratio M (25°C) 0.98, refractive index (25°C) 1
Diaminosilicone (8) with ゜405, amine equivalent (meq/mg) 3800; specific gravity (25°C) 0.9'8, refractive index (25°C)
1°407, amine equivalent (meq/mg) 1700 Diaminosilicone Table 2 The abbreviations in Table 2 have the following meanings.

PPG100O: Polyoxypropylene glycol with an average molecular weight of 1000 PPG2000: Polyoxypropylene glycol with an average molecular weight of 2000 PPG3000: Polyoxypropylene glycol with an average molecular weight of 3000 PEA100O: Polyethylene adipate with an average molecular weight of 1000 PEA100O: Polyethylene butylene adipate PEA with an average molecular weight of 2000 300O : Polybutylene adipate TGlooO with an average molecular weight of 3000: Triethylene glycol TG2000 with an average molecular weight of 1000 N average molecule! 2000 triethylene glycol TG3000: average molecular weight 3000 triethylene glycol MDI: 4.4'-diphenylmethane diisocyanate TOi 8 ! - Lylene diisocyanate I: Silicone oil ii with a dynamic viscosity of 10,000 centistokes (Cst); Silicone oil with a kinematic viscosity of 10,000 centistokes (Cst) Fluororesin: Polytetrafluoroethylene This Table-3
As can be seen, in Examples 1 to 12 of the present invention, the amount of wear was very small at 3.3 to 10.5 mg/1000 times. On the other hand, if no acidic substances are added to the brimer (
Comparative Example 1) and when no halogenating agent was added (Comparative Example 2), the wear amount was 689.

3 to 702.9/1000 times, which is very large. The reason why the amount of wear in the above examples is so small is that the halogenating agent in the primer applied to the EPDM base material halogenates the primer itself, and also halogenates the base material to reduce the intermolecular force between the two. Increase and improve adhesion,
Moreover, it is thought that this is because diamino silicone promotes the curing of polyurethane in the coating composition and imparts wear resistance to the coating film of the coating composition.

In addition, since the film of the adhesive composition of the present invention exhibits functions such as hydraulic properties, sealing properties, and solvent resistance mainly due to the cyclic dimethylsiloxane containing an acidic substance, it is suitable for attaching a molding to an automobile body. When used in double-sided tape, it exhibits sufficient resistance to solvents such as wax remover and gasoline.

In addition to using the adhesive composition of the present invention as a primer in the above examples, the adhesive composition can also be used as it is by applying it to an adherend.

[Effects of the Invention] The adhesive composition of the present invention has an effect that it has excellent adhesion to an adherend and can impart excellent abrasion resistance to the paint applied thereon. .

Claims (1)

[Claims] 1. An adhesive composition comprising a cyclic dimethylsiloxane, an acidic substance, a halogenating agent, and a diamino silicone having the following structure. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, l_1 and l_2 are each 2 to 6, and the amine equivalent is 30
It is 0-25000.