JPS60226571A - Unsaturated polyester resin composition for putty - Google Patents

Abstract

PURPOSE:The titled easily handleable composition having extremely improved leather application and yellowing, obtained by blending an unsaturated polyester resin having air drying properties with a specific amount of phenolic resin. CONSTITUTION:100pts.wt. unsaturated polyester resin having air drying properties is blended with (B) 0.005-0.50pts.wt. phenolic resin. The component A is obtained by reacting an alpha,beta-unsaturated dibasic acid with a polyhydric alcohol, an air-drying imparting agent, and, if necessary, a saturated polybasic acid to give an unsaturated polyester, followed by dissolving 100pts.wt. unsaturated polyester in 25-100pts.wt. polymerizable monomer to which a polymerization inhibitor is added.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an unsaturated polyester resin composition for use in putty.

(Prior art) Polyester putty is made by blending an unsaturated polyester resin, a cobalt-based accelerator, and a filler such as Merck, then curing it with an organic peroxide catalyst, and using it as an undercoat for automobiles and vehicle repairs. Widely used as a paint.

Polyester putty can be roughly divided into two types: repair putty using unsaturated polyester resin that has air-drying properties and sheet metal putty that does not have air-drying properties. The former can be applied thinly and is air-drying, so it can be used as a finishing putty.
Because of its good adhesion, it was usually puttyed to areas with severe unevenness. Recently, an air-drying sheet metal putty that combines the features of both has been put on the market, and is attracting attention as a putty that has air-drying properties, and demand is increasing.

However, because repair putty has an air-drying property, depending on how the putty is stored and handled, it may react with oxygen in the air and cause the putty surface to gel (skin) or become discolored (υ).
There is a problem of yellowing).

This not only promotes complete gelation of the putty and shortens its useful life, but also causes coating defects.

Conventionally, such drawbacks have been addressed by improving the unsaturated polyester resin, changing the accelerator, the stabilizer, etc. However, the former method has not been put into practical use because the improvements are limited to reducing drying properties, such as changing the air-drying agent.

On the other hand, the latter method involves adding a polymerization inhibitor to reduce the amount of cobalt soap, which is one of the accelerators, but this also reduces drying properties and delays gelation.

In addition, its use is limited because it degrades the properties of the putty, such as having a small skin-preventing effect.

(Object of the invention) The present invention provides an unsaturated polyester resin composition for putty that has improved the above-mentioned drawbacks.

(Structure of the Invention) The present invention provides an air-drying unsaturated polyester resin 10
0.005 to 0.005 to 0.005 to 0.00 parts by weight of phenolic resin.
This invention relates to an unsaturated polyester resin composition for putty containing 50 parts by weight.

The unsaturated polyester resin in the present invention has α.

An unsaturated polyester obtained by reacting a β-unsaturated dibasic acid, a polyhydric alcohol, an air-drying agent, and if necessary a saturated polybasic acid is usually converted into a polymerizable monomer with a polymerization inhibitor added. Obtained by dissolving. α.

As the β-unsaturated dibasic acid, maleic anhydride is used.

Maleic acid, fumaric acid, itaconic acid, etc. are used.

Saturated polybasic acids that can be used as necessary include phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, cepatic acid, trimellitic acid, pyromellitic acid,
Tetrahydrophthalic anhydride.

3.6-Nindomethylenetetrahydrophthalic anhydride.

Glutaric acid and the like are used.

Ethylene glycol is a polyhydric alcohol.

Propylene glycol, diethylene glycol.

Triethylene glycol, siglobylene glycol, 1
, 3-butanediol, 1,6-hexanediol, L
4-'/chlorhexanediol, neopentyl glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, nlupitol, hydrogenated bisphenol A, polybutadiene glycol, and the like are used.

As the air-drying agent, oil-based air-drying agents such as transesterified products of drying oils or semi-drying oils, and fatty acids of these oils are used. Furthermore, allylic air-drying agents such as trimethylolpropane mono- or diallyl ether, glycerin mono- or diallyl ether, allyl glycidyl ether, ethylene glycol monoallyl ether, and pentaerythritol mono-, di- or triallyl ether are also used. The above materials are polycondensed by a conventional method to obtain an unsaturated polyester.

Polymerizable monomers that dissolve this unsaturated polyester include styrene, chlorostyrene, divinylbenzene, tert-butylstyrene, styrene bromide, diallylphthalate, and methyl methacrylate.

Ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, ethyl acrylate, butyl acrylate,
Acrylic acid, β-hydroxyethyl methacrylate, β-
Ethyl hydroxyacrylate and the like are used. The amount of the polymerizable monomer used is not particularly limited, but is preferably 25 to 100 parts by weight per 100 parts by weight of the unsaturated polyester.

The phenolic resin used in the present invention includes:

1 m-cresol carbolic acid, resorcinol, m-methoxyphenol, m-ethoxyphenol, 3.5xylenol, polyfunctional phenol of bisphenol AS, op-cresol, xylenol, butylphenol, inglophenol, cyclopentenylphenol, octylphenol, nonylphenol, dodecyl Alkylphenols such as phenol, formalin, and acetaldehyde.

Formaldehyde and other aldehydes with hydrochloric acid and sulfuric acid.

It is obtained by polycondensation using a catalyst such as nitric acid, sodium hydroxide, or calcium hydroxide. The above-mentioned phenolic resin is used in an amount of 0.0% per 100 parts by weight of the unsaturated polyester resin. O
O is used in a range of 5 to 0.5 parts by weight. If the amount of phenolic resin is less than 0.0 O5 parts by weight, sufficient anti-skinning effect will not be observed, and if it exceeds 0.5 parts by weight, the gelation of the unsaturated polyester resin will be severely delayed. 1 In normal operations, curing failure may occur. It's to wake you up.

When using the unsaturated polyester resin composition of the present invention, organic peroxides, curing accelerators, retarders, curing accelerators, fillers, pigments, etc. that are well known to those skilled in the art may also be added. .

(Example) The following will be explained using comparative examples and examples. In the examples, "part" means part by weight, and "chi" means percent by weight.

Production of unsaturated polyester resin 650 parts of fumaric acid, 365 L of tetrahydrophthalic anhydride
21 parts of propylene glycol, 509 parts of diethylene glycol, 336 parts of linseed oil fatty acid, and 0.2 part of hydroquinone! The temperature was raised to 150°C while blowing cine active gas into a four-bottle flask, and after keeping it warm for 1 hour, the temperature was raised to 180°C to further advance the reaction, and at the same temperature the acid value reached 3.
The heating reaction was carried out until the temperature reached 0.0. After the reaction was completed, it was dissolved in 1030 parts of styrene to which 0.2 part of hydroquinone was added.

The obtained unsaturated polyester resin (A) has a heating residue of 6
5.5% by weight, viscosity (25°C Gardner) 6.3 seconds.

It showed an acid value of 19.

Comparative Example 1 To 100 parts of unsaturated polyester resin (A), 0.02 part of paratertiary butylphenol and 0.01 part of hydroquinone were added and mixed to prepare a resin (1) with a pot life of 15 minutes. Resin (to the Igloo part, 180 parts of talc (FS Talc: manufactured by Nippon Talc), 5.0 parts of cobalt 6-thioctenate, 0.1 part of dimethyl ayu 9F, 10 parts of titanium white, and 12 parts of styrene were mixed, and the mixture was mixed with a high-speed dissolver. Mix to make putty (11).
Take 150 copies into a C can, seal it, and leave it at room temperature for one use/
After opening for 2 days, the occurrence of skin rash and yellowing was examined.

Comparative Example 2 Resin (II) was prepared by adding 0.02 parts of hydroquinone to 100 parts of unsaturated polyester resin CA1.

Putty (III) was prepared in the same manner as in Comparative Example 1, and the occurrence of skin tension and yellowing was examined.

Example 1 Unsaturated 9″′″″′ tree 1(A)″°° part 11Cyl-″f
0.15 part of a phenol resin obtained by polycondensing phenol and formalin using a hydrochloric acid catalyst and 0.01 part of hydroquinone were added to prepare a resin composition (1).

Then, in the same manner as in Comparative Example 1, talc, 6% cobalt octenoate, dimethylaniline, styrene, and titanium white were blended to prepare Putty+II). This putty was also examined for skin tension and yellowing in the same manner as in Comparative Example 1.

Example 2 Unsaturated polyester resin (paratertiary butylphenol and formalin were added to 1100 parts of A1 using a hydrochloric acid catalyst)
A resin composition (fV) was prepared by adding 0.15 part of the phenol resin obtained by polycondensation and 0.01 part of hydroquinone, and a putty was prepared in the same manner as in Comparative Example 1.
The occurrence of skin rash and yellowing was examined in the same manner as above.

Example 3 To 100 parts of unsaturated polyester resin (A), 0.15 part of phenol resin obtained by polycondensation of m-cresol and formalin using a hydrochloric acid catalyst and 0.01 part of hydroquinone were added to form resin (V). was created. Next, putty (V) was prepared in the same manner as in Comparative Example 1, and putty was applied in the same manner as in Comparative Example 1.
The occurrence of yellowing was investigated.

The resins obtained in the above Examples and Comparative Examples (JIS K 6) were added with 1.0 parts by weight of cobalt 6-thioctenate and 2.0 parts by weight of 55-methyl ethyl ketone peroxide.
The room temperature curing time (pot life) was measured according to 901. Also, for putty (Il~(V)), 1 for putty
．． Add 0 weight of methyl ethyl ketone peroxide and add 2
The drying property (≠150 sandpaper stops clogging) was examined at 5°C.

Table 1 shows the results of Examples and Comparative Examples.

Table 1 1) Keltime = 6 Cobalt thioctenate A dimethyl phthalate solution of 155 methyl ethyl ketone peroxide was added at x/z (11) and measured according to JIS K 6901.

2) Drying property: At 25°C, add 1 part of dimethyl phthalate solution of 55 dimethyl ethyl ketone peroxide to the putty.
Add sandpaper and apply it to a tin plate with a spatula to a thickness of about 2 to 3 mm. +150 Time (minutes) until the sandpaper will not get clogged.
It was shown in

3) Yellowing: The time (day) when the surface of the putty in the can started to turn yellow was defined as yellowing.

4) Skin-stretching: Skin-stretching was performed when the surface of the putty in the can had progressed to yellowing or when the surface of the putty directly gelled (8).

(Effects of the Invention) The putty obtained by the unsaturated polyester resin composition of the present invention has significantly improved skinning and prevention of yellowing without reducing drying properties.

This will greatly prevent the occurrence of skin blemishes due to poor storage or handling errors, making handling easier, and is expected to drastically reduce coating film defects.

Claims (1)

[Claims] 1. An unsaturated polyester resin composition for putty, comprising 100 parts by weight of an air-drying unsaturated polyester resin and 0.005 to 0.50 parts by weight of a phenolic resin.