JP3033610B2 - Adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive used for attaching a film or a metal foil to the surface of a molded article of a polymer material such as polycarbonate, urethane RIM, FRP, which tends to generate gas from the surface thereof over time. The present invention relates to an agent composition. More specifically, the present invention relates to a pressure-sensitive adhesive composition in which the film or the like does not bulge or peel due to gas (outgas) generated from the adherend to which the film is stuck.

[0002]

2. Description of the Related Art Urethane RIM and FR which have a short time after molding
It is known that P (polycarbonate) generates gas (outgas) from its surface. Therefore, the pressure-sensitive adhesive film attached to the surface has a drawback that gas is accumulated at the interface due to gas (outgas) generated from the adherend, causing blistering or peeling of the pressure-sensitive adhesive film. As a countermeasure, for example, Japanese Patent Application Laid-Open No. 61-141377 proposes a marking material comprising a continuous porous plastic film as a base material and an adhesive applied thereto.

[0003]

However, in the above method of using a continuous porous plastic film and letting out gas out, it is difficult to form a continuous porous material in a metallized film and for a transparent marking material because of its appearance. Could not be applied.

An object of the present invention is to provide a pressure-sensitive adhesive which does not cause peeling or blistering when a film or a substrate is adhered to an outgas generating adherend.

[0005]

Means for Solving the Problems The present invention has been intensively studied to achieve the above object, and as a result, the pressure-sensitive adhesive layer is made firm and tough and the adhesive strength is increased, so that the specific composition and the specific molecular weight can be reduced. The present invention was completed by finding that an adhesive obtained by reacting a specific amount of polyglycidylamine and zinc naphthenate with an acrylic copolymer having the same effectively prevents outgassing. That is, the present invention relates to an alkyl acrylate having 4 to 12 carbon atoms in an alkyl group having 0.1 to 10 parts by weight of an α, β unsaturated carboxylic acid.
Parts by weight and a vinyl monomer 0 copolymerizable with the above monomer
0.02 to 0.9 parts by weight of polyglycidylamine and 0.01 to 0.01 parts by weight of zinc naphthenate to 100 parts by weight of an acrylic copolymer consisting of 49.9 parts by weight
It relates to a pressure-sensitive adhesive composition mixed with 0.5 part by weight, and particularly preferably to the above-mentioned pressure-sensitive adhesive composition wherein the weight average molecular weight of the acrylic copolymer is from 200,000 to 400,000.

The α, β-unsaturated carboxylic acids forming the acrylic copolymer of the present invention include, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and the like.

The amount of the α, β-unsaturated carboxylic acid used is 0.1.
It needs to be 1 to 10% by weight, and a range of 2 to 7% by weight is particularly preferable.

If the amount of the α, β-ethylenically unsaturated carboxylic acid used is less than 0.1% by weight, the resulting pressure-sensitive adhesive has insufficient cohesive strength and heat resistance, and if it exceeds 10% by weight. , The stickiness becomes worse.

When the carbon number is 4 to 12, (preferably 4 to
Examples of the alkyl acrylate 8) include butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and lauryl acrylate. Of these, butyl acrylate is particularly preferred. Usage is 50-9
It must be 9.9% by weight, with a range of 70-95% by weight being particularly preferred. If it is less than 50% by weight, no adhesive strength is obtained.
Examples of the vinyl monomer copolymerizable with the above monomer include alkyl acrylate, vinyl acetate, styrene, acrylonitrile, N-vinylpyrrolidone and the like, and methyl acrylate is particularly preferred. The used amount of the vinyl compound needs to be 0 to 49% by weight, and particularly preferably 10 to 37% by weight. If the amount of the vinyl compound exceeds 49% by weight, the obtained adhesive strength is not sufficient, and the adhesive strength particularly at low temperatures is deteriorated.

The weight average molecular weight of the acrylic copolymer of the present invention is from 20 to 40 in consideration of the balance between secondary crosslinking and performance.
It is even more preferably 280,000 to 360,000. If the molecular weight is too high, gelation tends to occur due to secondary crosslinking, and if the molecular weight is too low, performance as a pressure-sensitive adhesive is not obtained.

[0011] The polyglycidyl amines for use in the present invention N, N, N', N'Tetoragurishiji Le - m-xylylenediamine, N, N-diglycidyl aniline,
N, N, N ', N', N " -pentaglycidyldiethylenetriamine , N, N-diglycidyltoluidine and the like can be mentioned. The addition amount must be 0.02 to 0.9 part by weight, and particularly preferably 0.05 to 0.2 part by weight, per 100 parts by weight of the acrylic copolymer. 0.
If the amount is less than 05 parts by weight, the cohesive strength is insufficient, and if it is more than 0.2 parts by weight, the adhesive strength is reduced and blistering is caused. The zinc naphthenate those of zinc content 10% shall be further secondary crosslinking in the presence of poly grayed Rishijiruamin 0.0
1 to 0.5 parts by weight, especially 0.1
-0.3 parts by weight is preferred.

When the amount is less than 0.01 parts by weight, generation of outgas cannot be sufficiently suppressed. On the other hand, if the amount exceeds 0.5 parts by weight, it gels immediately and cannot be applied.

[0013]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples.

Example 1 1- butyl acrylate (hereinafter referred to as
Abbreviated as "BA". ) / Methyl acrylate (hereinafter, referred to as
Abbreviated as "MA". ) / Acrylic acid (hereinafter, “AA”)
Abbreviated. ) = 70/25/5 solution polymerized weight average molecular weight Mw = 28 million in N to acrylic copolymer 100 parts by weight of, N, N', N'-tetraglycidyl meta key <br/> Shi Li Range 0.4 part by weight of an amine was added, and 0.05 part by weight of zinc naphthenate having a zinc content of 10% was added before coating. This mixture was coated on silicon release paper and dried at 100 ° C. for 2 minutes. The thickness of the pressure-sensitive adhesive layer after drying was 30 μm. A transparent soft PVC film having a thickness of 50 μm was laminated on the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive sheet. 1m of this adhesive sheet
polycarbonate plate having a thickness of m lamination to (Mitsubishi Rayon Co., Ltd. Dia Light P-1001) 100 ± 2 ℃
After storing in an oven for 3 hours, the adhesive strength, creep characteristics and appearance change were observed. The results are summarized in Table 1.

(Adhesive force): This adhesive film was coated on a polycarbonate plate (Dialite P-1 manufactured by Mitsubishi Rayon Co., Ltd.).
001), and the adhesive strength of the adhesive film after standing at room temperature (21 ± 2 ° C., 65 ± 5% RH) for 24 hours is measured by the method of JIS Z-0237.

(Creep property): This adhesive film was bonded to a polycarbonate plate (Dialite P-1001 manufactured by Mitsubishi Rayon Co., Ltd.), left at room temperature for 24 hours according to JIS Z-0237, and then placed in an oven at 80 ° C. The degree of misalignment or the time to drop when a load of 1 kg was allowed to stand for 15 minutes was measured. However, the base of the adhesive film at this time is a 25 μ polyester film (manufactured by 3M).

Example 2 Isooctyl acrylate
(IOA) / AA = 96/4 , 100 parts by weight of an adhesive having a weight average molecular weight Mw = 350,000, and N, N, N
Example 4 0.4 part by weight of N ', N'-tetraglycidyl meta-xylylenediamine was added, and 0.05 part by weight of zinc naphthenate (zinc content 10%) was added. This mixture was applied on a silicon release paper. A pressure-sensitive adhesive film was prepared in the same manner as in Example 1, and the appearance change and the like were measured.

Example 3 In Example 1, BA / M
Except for A / AA = 50/40/10, all tests were carried out in the same manner as in Example 1, and data were measured.

Embodiment 4 In Embodiment 1, N, N,
The test was carried out in the same manner as in Example 1 except that the amount of N ', N'-tetraglycidyl meta-xylylenediamine was changed to 0.02 parts by weight, and data was measured.

Embodiment 5 In Embodiment 1, N, N,
Example 1 except that the addition amount of N ', N'-tetraglycidyl meta-xylylenediamine was changed to 0.9 parts by weight.
The test was performed in the same manner as described above, and the data was measured.

Example 6 A test was conducted in the same manner as in Example 1 except that 0.01 part by weight of zinc naphthenate (10% zinc content) was added, and data was measured.

Example 7 A test was carried out in the same manner as in Example 1 except that 0.5 part by weight of zinc naphthenate (zinc content 10%) was added, and data was measured.

Example 8 A test was carried out in the same manner as in Example 1 except that an acrylic copolymer having a weight average molecular weight of 200,000 was used, and data was measured.

Example 9 A test was carried out in the same manner as in Example 1 except that the acrylic copolymer having a weight average molecular weight of 400,000 was used, and data was measured.

Comparative Example 1 In Example 1, BA / M
Example 1 except that A / AA = 48/47/5
The test was performed in the same manner as described above, and the data was measured.

Comparative Example 2 In Example 1, BA / M
The test was carried out in the same manner as in Example 1 except that A / AA = 64/25/11, and data was measured.

Comparative Example 3 In Example 1, BA / M
The test was carried out in the same manner as in Example 1 except that A / AA = 74.95 / 25 / 0.05, and data was measured.

Comparative Example 4 An experiment was carried out in the same manner as in Example 1 except that the weight average molecular weight of the polymerized acrylic copolymer was changed to Mw = 190,000, and data was measured.

Comparative Example 5 An experiment was carried out in the same manner as in Example 1 except that the weight average molecular weight of the polymerized acrylic copolymer was changed to Mw = 410,000, and data was measured.

Comparative Example 6 In Example 1, N, N,
An experiment was carried out in the same manner as in Example 1 except that the amount of N ', N'-tetraglycidyl meta-xylylenediamine added was 0.01 part by weight, and data was measured.

Comparative Example 7 In Example 1, N, N,
An experiment was carried out in the same manner as in Example 1 except that the amount of N ', N'-tetraglycidyl meta-xylylenediamine added was 1.0 part by weight, and data was measured.

Comparative Example 8 An experiment was carried out in the same manner as in Example 1 except that zinc naphthenate (zinc content: 10%) was changed to 0.005 parts by weight, and data was measured.

Comparative Example 9 An experiment was conducted in the same manner as in Example 1 except that zinc naphthenate (zinc content: 10%) was changed to 0.6 parts by weight, and data was measured. .

Comparative Example 10 In Example 1, an experiment was conducted in the same manner as in Example 1 except that only polyglycidylamine was added and zinc naphthenate was not added, and data was measured.

Comparative Example 11 In Example 1, an experiment was conducted in the same manner as in Example 1 except that only zinc naphthenate was added and polyglycidylamine was not added, and data was measured.

Comparative Example 12 The procedure of Example 1 was repeated except that the addition of polyglycidylamine and zinc naphthenate was stopped, and 1.0 part by weight of Coronate L (manufactured by Nippon Polyurethane Co., Ltd.) was added instead. An experiment was performed in the same manner as in Example 1 and data was measured.

From Table 1, it can be seen that the pressure-sensitive adhesive compositions according to the examples of the present invention do not have any abnormal appearance such as blisters, maintain a peel strength of 1.50 kg / 25 mm in all adhesive strengths, and have a creep property. In all cases, the composition was suppressed to 0.5 mm or less, indicating that the composition was superior to the composition of the comparative example.

[0038]

[Table 1]

[0039]

Since the pressure-sensitive adhesive composition according to the present invention has the above-mentioned constitution, it is possible to attach a film or a base material to an outgas generating adherend without particularly using a continuous porous plastic film. Does not cause peeling or blistering on the film or substrate. In addition, there is an effect that a transparent or metal-deposited film or substrate can be used.

Continuation of the front page (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 1/00-201/10 CA (STN) REGISTRY (STN) WPI / L (QUESTEL)

Claims (2)

(57) [Claims] 1. An α, β unsaturated carboxylic acid of 0.1 to 10 parts by weight, an alkyl group having 4 to 12 carbon atoms of an acrylic acid ester of 50 to 99.9 parts by weight and copolymerized with the above monomer. 0.02-0.9 parts by weight of polyglycidylamine and zinc naphthenate (zinc content 10%) are added to 100 parts by weight of an acrylic copolymer comprising 0-49.9 parts by weight of a vinyl monomer. A pressure-sensitive adhesive composition obtained by mixing 01 to 0.5 parts by weight. 2. The pressure-sensitive adhesive composition according to claim 1, wherein the weight average molecular weight of the acrylic copolymer is from 200,000 to 400,000.