JPH04198369A - Putty composition - Google Patents

Abstract

PURPOSE:To obtain the putty composition consisting of a main agent containing a specific unsaturated polyester, polymerizable diluent and filler and curing agent containing an organic peroxide and having excellent adhesion to a plastic material, aluminum, etc. CONSTITUTION:The objective composition consisting of (A) a main agent containing 100 pts.wt. unsaturated polyester resin obtained by reacting an essential component-containing raw material component obtained by blending alpha,beta-ethylene based unsaturated dicarboxylic acid (e.g. fumaric acid or maleic anhydride) and saturated polybasic acid (e.g. phthalic anhydride or adipic acid) with a polyhydric alcohol (e.g. ethylene glycol) at a wt. ratio of 1:2 to 4:3; (B) 20-60 pts.wt., preferably 30-40 pts.wt. polymerizable diluent (e.g. styrene); (C) 200-250 pts.wt., preferably 215-230 pts.wt. filler (e.g. talc); and (D) a curing agent containing an organic peroxide (e.g. benzoyl peroxide).

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a putty composition, and more specifically, it can be used for vehicles, architecture, etc., and is particularly effective for plastic materials, aluminum, etc. The present invention relates to a putty composition having adhesive properties and the like.

<Prior art> Various compositions based on nitrified cotton thread, acrylic type, aminoalkyd type, urethane type, unsaturated polyester type, etc. have been proposed as putty used for vehicles, construction, etc. , are used depending on the various applications.

In recent years, it has also been used as a material for automobiles, buildings, etc.

Plastic materials, aluminum materials, and the like have come into widespread use, and there is a demand for the development of putty suitable for repairing these materials.

However, with the putty that has been proposed and implemented in the past,
At present, it has insufficient adhesion to the plastic materials, aluminum materials, etc., and also has problems with impact resistance, weather resistance, etc., and has not been put into practical use.

<Problems to be Solved by the Invention> Therefore, an object of the present invention is to provide a cured product that has excellent adhesion to plastic materials and aluminum materials, and that the resulting cured product has excellent impact resistance, ozone resistance, An object of the present invention is to provide a putty composition having weather resistance.

<Means for Solving the Problems> According to the present invention, α, β-ethylenically unsaturated dicarboxylic acid, saturated polybasic acid, and polyhydric alcohol are mixed in a weight ratio of 1:2.
~4: Unsaturated polyester resin (A
) 20 to 6 parts by weight of polymerizable diluent (B) per 100 parts by weight
There is provided a putty composition comprising a main ingredient containing 0 parts by weight and 200 to 250 parts by weight of a filler (C), and a curing agent containing an organic peroxide (D).

The present invention will be explained in more detail below.

The putty composition of the present invention comprises a main ingredient containing a polymerizable diluent (B) and a filler (C) in a specific proportion to 100 parts by weight of a specific unsaturated polyester resin (A), and a specific unsaturated polyester resin (A). It is characterized by consisting of a curing agent.

The unsaturated polyester resin (A) used in the present invention is made by reacting raw material components containing essential components made by blending α, β-ethylenically unsaturated dicarboxylic acid, saturated polybasic acid, and polyhydric alcohol in specific proportions. A resin obtained,
Preferably, the resin has a weight average molecular weight of 1,000 to 10,000, particularly preferably 2,000 to 5,000. Said α,
Preferred examples of the β-ethylenically unsaturated dicarboxylic acid include fumaric acid, maleic anhydride, maleic acid, and itaconic acid, which can be used alone or as a mixture. Examples of the saturated polybasic acids include phthalic anhydride, phthalic acid, adipic acid, isophthalic acid, terephthalic acid, cepatic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic anhydride, benzoic acid, and paratertiary butylbenzoic acid. acid, 3,6
-Nindomethylenetetrahydrophthalic anhydride, glutaric acid and the like can be preferably mentioned, and they can be used alone or as a mixture. Further, examples of the polyhydric alcohol include 4f ethylene glycol,
Propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-
Butanediol, 1,6-hexanediol, 1,4-
Preferred examples include cyclohexanediol, neopentyl glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, hydrogenated bisphenol A, and polybutadiene glycol, which can be used alone or as a mixture. .

α, β- which are essential components of the unsaturated polyester resin
The mixing ratio of ethylenically unsaturated dicarboxylic acid, saturated polybasic acid, and polyhydric alcohol is 1:2 to 4:3 to 5 by weight.
The range is preferably 1:2.8 to 3.3:3.8
A range of ~4.3 is desirable.

In order to prepare the unsaturated polyester resin, for example, each raw material component is mixed and thermally polymerized by a known method, specifically, at a reaction temperature of 100 to 240°C for about 0.5 to 15 hours. I can do it.

The polymerizable diluent (B) used in the present invention is a component that dissolves the unsaturated polyester resin (A) and acts as a crosslinking agent, such as styrene, chlorostyrene, divinylbenzene, tert-butylstyrene, Styrene bromide, diallyl phthalate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, ethyl acrylate, butyl acrylate, acrylic acid, ethyl β-hydroxymethacrylate, ethyl β-hydroxyacrylate, etc. are preferred. They can be used alone or as a mixture. The blending ratio of the polymerizable diluent (B) in the main resin is in the range of 20 to 60 parts by weight, preferably 3 parts by weight, based on 100 parts by weight of the unsaturated polyester resin (A).
The range is 0 to 40 parts by weight.

Examples of the filler (C) used in the present invention include talc, titanium oxide, calcium carbonate, kaolin, clay, mica, finely divided silica, alumina, barium sulfate, gypsum, perlite, carbon black, graphite, cyanine blue, chrome yellow, Watching Red, Red Garla, Aniline Black, Manganese Blue, Iron Black, Ultramarine Blue, Hansa Red, Chrome Inirow,
Preferable examples include extender pigments and pigments such as chrome green and zinc stearate. In particular, when used for automobile repair, it is desirable to include talc.

The blending ratio of the filler (C) in the main resin is 200 parts by weight per 100 parts by weight of the unsaturated polyester resin (A).
-250 parts by weight, preferably 215-23 parts by weight
It is in the range of 0 parts by weight. Further, the filler (C) can be added to a curing agent to be described later, if necessary.

In the present invention, the organic peroxide (D) contained as a curing agent component is not particularly limited, and known examples such as benzoyl peroxide and peroxide can be used. In addition, from the viewpoint of storage stability and handling safety of the curing agent, an organic solvent such as diisobutyl phthalate may be added to the organic peroxide (D), and furthermore, iron dioxide, silica, etc. may be added to the organic peroxide (D). It is also possible to add other inorganic ingredients. The blending ratio when using the organic solvent is preferably in the range of 50 to 110 parts by weight, particularly 55 to 70 parts by weight, based on 100 parts by weight of the oxidized oxide (D). The amount is preferably in the range of 0 to 50 parts by weight.

In the putty composition of the present invention, in addition to the above-mentioned components, commonly used curing accelerators, retarders, curing accelerating aids, etc. can be appropriately contained as necessary.

In order to prepare the putty composition of the present invention, at the time of use, the main ingredient and the curing agent are mixed, for example, in a kneader or the like, preferably at a 0.
After mixing for about 5 to 3 minutes and applying it to the object to be coated, whose surface has been previously treated with sandpaper, etc., in the desired shape, the mixture is naturally dried for 10 to 30 minutes at room temperature (about 20°C). Obtainable. In this case, it is preferable that the blending ratio of the main ingredient and the curing agent is in the range of 1:0.03 to 0.1, particularly preferably 1:0.4 to 0.7 in terms of weight ratio.

<Effects of the Invention> The putty composition of the present invention has a main ingredient containing a specific unsaturated polyester resin (A), a polymerizable diluent (B), and a filler (C) in specific proportions as an essential component. Contains iron,
It has excellent adhesion not only to urethane, but also to plastic materials and aluminum materials, to which conventional putty has not had sufficient adhesion, and the resulting cured product has permanent flexibility, making it especially excellent. It has excellent impact resistance, ozone resistance, weather resistance, etc. Therefore, it is extremely useful as a putty for repair molding, thickening, finishing, etc. in vehicles and architecture.

<Examples> The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

In a flask equipped with an overhead stirrer, a thermometer, and a nitrogen gas blowing tube, add 34 parts by weight of phthalic acid, 12 parts by weight of fumaric acid, 4 parts by weight of adipic acid, 0.1 part by weight of hydroquinone, and 50 parts by weight of diethylene glycol. was charged and reacted at 180 to 200°C for 4 hours while introducing nitrogen gas to obtain an unsaturated polyester resin (A) having a weight average molecular weight of 3410.

Next, 100 parts by weight of the obtained unsaturated polyester resin (A), 35.7 parts by weight of styrene, and 221.5 parts by weight of talc.
Parts by weight were uniformly mixed to prepare a main ingredient. Separately, 48 parts by weight of benzoyl peroxide, 30 parts by weight of diisobutyl phthalate, and 22 parts by weight of triferric oxide containing a trace amount of silica were mixed and stirred in a glass beaker to prepare a curing agent. Next, 100 parts by weight of the obtained main agent and 5 parts by weight of the curing agent were mixed to produce a putty composition, and then a polypropylene plate (70 x 150 x 5 mm) and an aluminum plate (70
x 150 x 5 mm) so that the thickness after curing would be 5 m, and was cured at room temperature for 15 minutes to prepare a test piece. In addition, the end of the test piece was shaved with a knife to prepare a thin film portion with a thickness of 2 mm.

Impact resistance tests, adhesion tests, flying stone tests, ozone resistance tests, and accelerated weather resistance tests were conducted on each of the obtained test pieces. The test method is shown below, and the test results are shown in Table 1.

[JIS K5400 8.3, 2. The height at which cracking and peeling occurred is shown as the result.

11 Works X Supervision JIS K5400 8.7 r Paint General Test Method”
I followed.

Flying stone test JASo 7320 r brake tube test method”
5.4, air pressure 1 kg/ad and 4 kg/ad
I went with d. However, the size of crushed stone is 5-13III11 (
No. 6 crushed stone), and the amount of crushed stone used was 250 g.

The results are for the thin membrane part (thickness 2m+) and the normal membrane part (thickness 5m).
mm) with no cracks or peeling observed.
Those that were slightly observed were rated △, and those that were slightly observed were rated X.

Created and supervised by 1tJy JIS A 6021 5.8.2. The test was carried out for 7 days using "Roof Paint Film Waterproofing Agent". However, the ozone concentration is 75±
The temperature was 7.5 pphm and 40±2°C. Result is,
Those in which no abnormality was observed were rated O.

The test was conducted for 300 hours in accordance with ``General Test Methods for Paints'' (1 JIS K5400 9.8.1.r).The results are as follows.

Those in which no abnormality was observed were rated O.

(Margin below)

Claims (1)

[Claims] A raw material containing essential components made by blending α,β-ethylenically unsaturated dicarboxylic acid, saturated polybasic acid, and polyhydric alcohol in a weight ratio of 1:2 to 4:3 to 5. A base agent containing 20 to 60 parts by weight of a polymerizable diluent (B) and 200 to 250 parts by weight of a filler (C) based on 100 parts by weight of an unsaturated polyester resin (A) obtained by reacting the components; A putty composition comprising a curing agent containing an organic peroxide (D).