JPS5827751A - Molding composition for frp - Google Patents

Abstract

PURPOSE:The titled composition that is prepared by previously adding a liquid paint free from water or a solvent, thus being suitably used for molding FRP products which have high smooth surfaces and permit surface coating without formation of skims and pinholes. CONSTITUTION:The resin component containing an unsaturated polyester resin as the major constituent (15-60wt%), a reinforcing material such as glass fiber of 2-30mu diameter and 5-50mm. length and a filler such as calcium carbonate (15-60wt%), a catalyst such as t-butyl perbenzoate (0.01-5wt%), a liquid paint free from water and a solvent (namely its major resin is liquid such as an epoxy resin and it is combined with a curing agent, pigments and additives, containing more than 98% nonvolatile components) (0.3-20wt%) are kneaded by means of, e.g., a Henschel mixer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a molding composition for FRP, and more specifically to an FRP article that has excellent surface smoothness and can be coated with an M film on the surface without wrinkles or pits that cause pinholes. The present invention relates to a molding composition for FRP suitable for molding.

FRP (Fib@rwork1nforcsd Plist
lcm) #i was originally developed as an extremely strong material made by filling unsaturated polyester resin with glass fibers, and has been applied to other thermosetting resins and even thermoplastic resins.

FRP has mechanical strength per unit weight that is stronger than general metal materials, and it is also heat resistant and cold resistant as a material that can make products that are lighter and stronger than metals.

As a material with excellent physical properties such as weather resistance and moldability, it is widely used in various structural materials, automobile parts, exterior materials, etc. Particularly in recent years, in order to improve workability and productivity, reinforcing materials such as glass fibers are pre-impregnated with resin and other fillers and hardening agents.
Molding containers for OF'RP in a dry semi-cured state such as SMC, TMC) and block or rod shapes (BMC) have been developed and are widely used for molding FRP articles.

By the way, since FRP products have poor surface smoothness, or to further improve their appearance, weather resistance, abrasion resistance, etc.
Painting is performed on the surface of FRP articles. Such coating is also necessary when, for example, in the case of automobile parts, it is necessary to paint the parts in a desired color to match the color scheme of the entire automobile or to coat them integrally with the automobile body. However, when conventional solvent-based paints are applied to FRP articles, there are many problems such as foaming during the baking process, which often causes cracks and pinholes in the paint film, which impairs the performance and appearance of the paint film. It is assumed that this problem is caused by the fact that air, other gases, and volatile components are present in the FRP article and are released to the outside during the paint baking process. Also, F.R.
Even when a urethane-based material such as 2-Imager is applied on the P article, the above-mentioned foaming phenomenon during baking is not improved, and the FRP
Even when applying pliers to the product and then applying solvent-based paint, it is easy to cause wrinkles during baking.Furthermore, when molding FRP, the surface opposite the folds or protrusions of the molded product may be slightly wrinkled. This phenomenon is thought to occur due to uneven shrinkage of the molding material. If a solvent-based paint is applied over this "sink mark", the paint film will have a step difference along the "sink mark", which will spoil the aesthetics.Furthermore, another problem is that when applying a solvent-based paint on top of a layer, One of the reasons is that electrocoating is difficult.

'This is thought to be due to the extremely high electrical resistance of the smooth surface.

Therefore, the inventors of the present invention have conducted repeated research to solve the above-mentioned problems in the coating technology for layered products, and have succeeded in coating the products using a special technique without creating wrinkles or pinholes on the surface. However, after further investigation, the inventors discovered that the above-mentioned problems could be effectively solved by incorporating a liquid paint containing water or a solvent into the molding compound in advance, thereby achieving the present invention. Thus, the molding composition according to the present invention has a resin content of 15 to 60 wt - 1 reinforcement 15 to 60 wt - 1 filler 15 to 60 wt - 1 catalyst 0.01 to 5 wt - and water. and 0.3 to 20% by weight of a solvent-free liquid paint.

The resin component to be blended into the composition of the present invention includes any resin commonly used in conventional molding compounds, such as unsaturated I-lyester resins, diallyl phthalate resins, etc. as main components, and poly(meth) Acrylate resin% I listyrene, saturated I reester resin, styrene monoff-, (meth)acrylic mono i-
etc. can be used. These resins can be used alone or in combination. These resins are based on the total weight of the composition.
915-60% by weight, preferably 20-50% by weight 911
Use within the range. If the amount of resin blended is too large,
[, 'fMc, EMC-&' This is not preferable because it becomes difficult to maintain the shape and the strength of FRP is low.On the other hand, if the blending amount is too small, the fluidity during molding will be poor and the surface of the layer will be This is not preferred because the smoothness is poor.

The reinforcing material (or reinforcing material) to be incorporated into the composition of the present invention may be any reinforcing material commonly used in conventional molding compounds, such as glass having a diameter of about 2 to 30 μm and a length of about 5 to 50 μm. Fibers, carton fibers, etc. can be used.

These reinforcing materials may be used alone or in combination.These reinforcing materials are used in an amount of 15 to 60% by weight, preferably 20 to 50% by weight, based on the total weight of the composition. If the amount of reinforcing material blended is too large, molding becomes difficult and fluidity decreases, which is undesirable.On the other hand, if the blended amount is too small, the strength of the layer decreases, which is not preferable.

Fillers to be incorporated into the composition of the present invention include any fillers commonly used in conventional molding compounds, such as powder fillers such as calcium carbonate, barium sulfate, talc, kaolin, clay, and silica powder. can be used. These fillers can be used alone or in combination. These fillers are used in an amount of 15 to 60% by weight, preferably 20 to 50% by weight, based on the total weight of the composition. If the amount of filler blended is too large, the strength will decrease and molding will become difficult, which is undesirable.On the other hand, if the blended amount is too small, the shrinkage rate will be large when cooling the molded product after molding. SMc, TMC.

This is not preferable because it becomes difficult to maintain the shape of the sample.

The catalyst (or curing agent) used in the composition of the present invention may be any catalyst commonly used in conventional molding compounds for nQ, such as t-butyl perbenzoate, penzoyl oxide, t-butyl perbenzoate, etc. A peroxide that decomposes at a temperature of 100 to 160°C, such as arm oxide, can be used. These catalysts can be used alone or in combination. These catalysts are used in an amount of 0.01 to 5 weight percent, preferably 0.1 to 2 weight percent, based on the total amount of the composition.
Use within a range of weight. If the catalyst blend I is too large, the flow time of the compound will be shortened, making molding difficult, which is undesirable.On the other hand, if the blending quantity is too small, the resin will not be sufficiently cured and its strength will decrease. So I don't like it.

The molding composition for FRP of the present invention includes the above-mentioned n
In addition to the general formulation ingredients of ``, a liquid paint that does not contain water or solvent is formulated. The liquid coating material that can be used in the present invention is a coating material that is substantially free of water and solvents and contains, for example, a liquid synthetic resin, a phenolic compound, a complex aionic compound, an imidazole compound, and an adenoresin as main components. Such a paint itself is already known. It should be noted that if water and solvent are contained, the water and solvent will volatilize during compression molding, which is undesirable because pinholes and cracks will occur on the surface of the flying object.

The liquid paint mentioned here is one in which the main resin is liquid, a liquid or solid curing agent, and if necessary, pigments, additives, and curing accelerators, and the non-volatile content is 98%.
This refers to the above.

As the resin, for example, liquid epoxy resin, liquid acrylic resin, etc. can be used. As a curing agent, one that reacts with the above-mentioned resin is used, for example, in the case of an epoxy resin, the above-mentioned curing agent is used, and in the case of an acrylic resin having an OH group, a melamine resin is used.

In the case of an acrylic resin having a glycidyl group, dicargenic acid, an acid anhydride, etc. can be used, and in the case of an acrylic resin having a calgexyl group, an epoxy resin or an oxazoline compound can be used. It is preferable that these combinations do not produce reaction products during the curing reaction. These compositions include known inorganic pigments, organic pigments,
Additives can be added.

These liquid paints are used in an amount of 0.3 to 20% by weight, preferably 1 to 20% by weight, based on the total weight of the composition. If the amount of liquid paint is too large, it will not be possible to maintain the shape of y or B, and the strength of the molded FRP will decrease, which is undesirable.On the other hand, if the amount of liquid paint is too small, solvent-based paint will be applied to the product. This is undesirable as it will cause wrinkles and pinholes if painted.

In addition to the above-mentioned essential components, the FRP molding composition of the present invention includes commonly used optional components such as pigments, crystal nucleating agents, plasticizers, mold release agents, lubricants, heat stabilizers, antioxidants, and ultraviolet absorbers. Agents, flame retardants, polymerization inhibitors, etc. can be added.

The molding composition used in accordance with the present invention is a conventional FR molding composition.
It can be prepared into any shape such as a sheet, a block, or a rod by the same method as the P molding compound Δ round. To illustrate one example of such a preparation method, a resin, water and solvent-free liquid paint, filler, catalyst and other compositions are uniformly mixed in a Henschel mixer and then impregnated with a reinforcing agent to form tiles. you can get
In addition, by inserting this core between two sheets of polyethylene and rolling it with a roll to an appropriate thickness, for example, a thickness of 3 mm, a hole can be obtained. These assays and gMC are e.g.
It can also be used after being aged for 48 hours at 0°C.

The molding composition for FRP according to the present invention is generally applied in advance with a mold release agent to a mold having a desired shape, and then applied in a predetermined amount in the form of a sheet or cut, or in the form of a lump or rod. It can be charged and compression molded using a compression press using a general method.

Compression molding should be carried out under conditions that are almost the same as general FRP molding conditions, or for a medium or long time compared to general layer molding conditions in order to ensure that the liquid paint components are completely cured in the FRP product. I can do it.

For example, temperature 120-160℃, pressure 3-100kf/
.

Furthermore, the compression molded FRP is further
It can also be sufficiently hardened by baking at a temperature of 1 to 30 minutes.

In this way, if the molding composition for I of the present invention is used, a coating film can be formed without the problem of "sink", with excellent surface smoothness, and without the generation of wrinkles or pinholes on the surface. A layered article can be obtained. This product has sufficient surface smoothness, weather resistance, and
It has various properties such as abrasion resistance, but in order to further enhance the aesthetic appearance and provide other desired properties, a solid color or metallic color is applied on top of the liquid paint film according to a conventional method. Paints (for example, solvent-based paints) can be suitably applied as a top coat. In addition, Kagenpla, resin, and graphite are added to the liquid paint.

For example, 1 to 2 conductive substances such as zinc powder or antistatic agent are added.
By blending at 0 weight, the top coat can be electrostatically applied easily and effectively.

Hereinafter, the present invention will be explained in more detail according to Examples.
It goes without saying that the present invention is not limited to these examples. In the following examples, "parts" are "parts by weight"
shows.

Example 1 Unsaturated polyester resin (Shikinichi Yakuhin Polymer 64
09) 30 parts, calcium carbonate powder (Whiten B manufactured by Shiraishi Calcium) 40 parts, t-butyl nobenzoate 0
．． 3 parts of zinc stearate, 1 part of polyethylene powder, 1 part of magnesium oxide powder, and 5 parts of a prescribed paint were mixed for 1 minute in a Henschel mixer. This mixture was spread on a 0.05 inch thick polyethylene sheet to a thickness of about 5 m, and 30 parts of glass fiber (
(15μ in diameter and 26μ in length) was placed uniformly on the drawn mixture to impregnate the glass fibers with the mixture. Further, a 0.05 m thick ethylene sheet was placed on top of this and passed through a roll to obtain a sheet composition with a thickness of 3 mm. This sheet-like composition was wrapped in aluminum foil and aged by keeping it at 46° C. for 48 hours to obtain the required molding compound/4 land.

The interior is made of stainless steel with a thickness of 6 parts, width of 1,505 wm, and length of 200 m+, with a top surface of 160°C and a bottom surface of 145"C.
It was heated in a heated oven adjusted to . After applying a mold release agent (Mirror Glide Poly, Mirror Glaze manufactured by Shu) to the inner surface of the mold, apply the required molding compound Δ round 3.
5ON was charged and compression molded for 8 minutes at a pressure of 30 kIi/-. The molded product was removed from the mold, and the surface of the molded product was heated and molded at 160°C.
000G-50 Shedland White NH-61) 3
5μ spray painting, 150℃ after setting for 10 minutes
Baked for 20 minutes. Table 1 shows the appearance after molding and after painting with solvent paint.

Table 1 (Note 1) 100 parts of Epicor 828 (liquid epoxy resin manufactured by Shell Chemical), 3 parts of 2-undecylimidazole,
Carganbula, 1 part resin and titanium oxide (manufactured by Bancho Sangyo R-
820) Paint prepared by mixing 10 parts in a conventional manner (Note 2) Paint prepared by mixing 100 parts of 82 g of Epicoat, 8 parts of dicyandiamide, 1.5 parts of 2-methylimidazole, and 1.5 parts of carbon black in a conventional manner. .

(Note 3) 100 parts of liquid acrylic resin (an acrylic resin with a number average molecular weight of 4500 consisting of 27 parts of glycidyl methacrylate, 50 parts of n-butyl acrylate, and 23 parts of 2-ethylhexyl acrylate), finely pulverized 1.10 parts
Decanedicargenic acid 20 parts, dibutyltin oxide 0
．． A coating material prepared by mixing 5 parts of Carganpla and 2 parts of resin using a conventional method.

(Note 4) Appearance after molding ◎: Excellent smoothness ○: Good smoothness Δ: Slightly poor smoothness ×: Poor smoothness (Note 5) Armpit after painting with solvent-based paint ◎: Abnormalities such as armpits Very good with no defects ○: There are almost no abnormalities such as underarms.
A melamine alkaline paint consisting of 15 parts titanium oxide and 55 parts solvent.

Example 2 Instead of the required molding compound Δ round used in Example 1, a layer agent molding compound/container land having the following composition was manufactured in the same manner as in Example 1.

Unsaturated? Reester resin (Shikinichi Pharmaceutical Polymer 64
09) 40 parts calcium carbonate powder (Whiten B manufactured by Shiraishi Calcium) 20 parts talc 10 parts tert-butyl 7-benzoate 0.5 parts zinc stearate 0.5 parts polyethylene powder 0.5 parts magnesium oxide powder 1 part paint
10 parts glass fiber (diameter 15μ and length 2
6m) or more for a composition of 65 parts
Part 35: A mold for manufacturing a T-shaped molded product with the shape and dimensions shown in Fig.
The lower side was heated to 145°C. After applying a mold release agent to the inner surface of the mold, the above-mentioned required molding cone mother land 350 is applied.
No. 11 was charged and compression molded for 8 minutes at a pressure of 30 Y/-. The constituent products were removed from the mold, and the surface of the molded product heated and molded at 160°C was painted with 35 μ gray solvent-based paint (same as in Example 1), and after heating for 10 minutes, it was heated at 150°C. , baked for 20 minutes. The second appearance after molding and painting with solvent-based paint! ! Shown below.

Margin below

[Brief explanation of the drawing]

Figure 1 shows the molded products in Examples and Comparative Examples of the present invention.
2 is a drawing showing the shape and dimensions of a T-shaped molded product for testing the presence or absence of sink marks. Patent applicant Nippon Into Co., Ltd. Patent agent Akira Aoki Patent attorney Kazuyuki Nishidate Patent attorney Ishi 1) Honorable patent attorney Akiyuki Yamaguchi

Claims (1)

[Claims] 1. Resin content 15-60% by weight, reinforcing material 15-60% by weight 2.
．． A molding assembly for FRP comprising a filling material of 15 to 60 parts by weight, a catalyst of 0.01 to 5 parts by weight, and a liquid paint containing no water or solvent of 0.3 to 20 parts by weight. 2. The composition according to claim 1, wherein the resin component contains an unsaturated polyester resin as a main component. 3. The liquid coating material according to claim 1 or 2, wherein the liquid paint contains as main components a liquid epoxy resin and at least one of a phenol compound, a complex amine compound, an imidazole compound, and an adenoresin. Composition.