JPH01101248A - Decoration or protective member for automobile - Google Patents

Abstract

PURPOSE:To enable reduction in aging of color tone and hardness of colored coating applied on the surface exposed outdoor over a long period by forming a resin composition composed of thermoplastic polyurethane of a non-yollowing type combined or uncombined with polymer of a vinyl chloride family and of pigment. CONSTITUTION:This resin composition must be polymer of a vinyl chloride family, thermoplastic polyurethane of a non-yellowing type, in other words, it must be composed of thermoplastic polyurethane wherein polysocyanate of an aromatic family as polysocyanate of law material is not used in selecting material out of thermoplastic polyurethane of any type, and of pigment. However, it is allowed whether polymer of a vinyl chloride family is chemically combined with thermoplastic polyurethane of a non-yellowing type or not within resin composition. As resin composition, either of already known polymer of a vinyl chloride family such as, for example, Aron NP-6000 or DOEMINASK700 and the like available on the commercial market and resin composition composed of thermoplastic polyurethane of a non-yellowing type can be used, and color tone and hardness of the surface of a formed molding and the like changing with time can be restrained.

Description

Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention relates to decorative or protective materials for automobiles made of synthetic resin molded articles, such as moldings attached to the body of automobiles. be.

[Conventional technology]

In automobiles, moldings made of synthetic resin such as soft vinyl chloride resin, generally called side protection moldings, window moldings, or end protection moldings, are attached for the purpose of decoration and/or protection of the vehicle body.

As the needs of buyers regarding the design of automobiles become more diverse, decorative or protective materials for automobiles such as moldings are also required to have a variety of colors.

For example, in the past, black moldings using carbon paint as pigments were exclusively used as moldings for automobiles, but recently, moldings in colors other than black, such as white and cream, are being used to match the color of the car body. The use of moldings is becoming popular.

Generally speaking, there are two methods for coloring moldings: using a resin compound containing pigments, as is used for conventional black moldings, and painting resin moldings with colored paint after molding. Usually, colored molding made by the former method is called a dyed molding, and colored molding made by the latter method is called a painted molding.

However, moldings colored by any of the above methods have the problem that the color tone changes over time if they are used in a car for a long time. , Spring type hardness tester A according to JISK6501
This was particularly noticeable in moldings in which an iron core was embedded in a soft resin having a hardness (hereinafter abbreviated as JIS A hardness) of about 70 to 75 (A) as measured by the shape.

Furthermore, in primary color moldings, in addition to the change in color tone of the surface of the molding over time, there is also the problem that the hardness of the resin molded article progresses over time, making it impossible to maintain the desired initial hardness.

Since the production cost of a dyed molding is lower than that of a painted molding, there is a great demand for it as a general-purpose colored molding, and therefore there is a strong desire to solve the above-mentioned problems in a dyed molding.

[Problem that the invention seeks to solve]

The present invention is directed to the above-mentioned raw material, which has small changes over time in color tone on the surface of the molded product and small changes over time in hardness of the molded product, and has excellent moldability, weather resistance, water resistance, etc., and good mechanical properties. The object of the present invention is to provide a decorative or protective equipment for automobiles made of a molded article of a colored resin compound containing a pigment, such as a colored molding.

(B) Structure of the Invention [Means for Solving the Problems] The present invention relates to vinyl chloride monomers, vinyl chloride monomers, vinyl monomers copolymerizable with the same, and vinyl monomers copolymerizable with the vinyl chloride monomers. Vinyl chloride polymers obtained from monomer mixtures with monomers (hereinafter collectively referred to as vinyl chloride monomers), non-yellowing products that may or may not be chemically bonded to vinyl chloride monomers. This is a decorative or protective material for automobiles formed by molding a resin composition consisting of thermoplastic polyurethane and a pigment.

The present invention will be explained in more detail below.

The resin composition of the present invention is composed of a vinyl chloride polymer, a non-yellowing thermoplastic polyurethane, that is, a thermoplastic polyurethane that does not use an aromatic polyisocyanate as a raw material polyisocyanate among thermoplastic polyurethanes, and a pigment. However, in the resin composition, the vinyl chloride polymer and the non-yellowing thermoplastic polyurethane may be chemically bonded, or may not be chemically bonded.

Examples of resin components in such resin compositions include:
Commercially available vinyl chloride polymers such as Aron NP6000 (trade name, manufactured by Toyaku Gosei Chemical Industry Co., Ltd.) or DOMINASK700C (trade name, Toyo Soda Chemical Industry Co., Ltd.), which are already generally known or used, and non-yellowing. Any resin composition made of thermoplastic polyurethane can be used, and they can be classified according to their manufacturing method as follows, such as fat to lb1.

(a) A resin composition formed by blending a vinyl chloride polymer and a non-yellowing thermoplastic polyurethane.

Tb) A resin composition obtained by adding a non-aromatic polyisocyanate to a polyol-impregnated vinyl chloride polymer to form a non-yellowing thermoplastic polyurethane in the vinyl chloride polymer (Japanese Patent Publication No. 59-39464) Publication No.)
.

lcj A resin composition obtained by polymerizing a vinyl chloride monomer in an aqueous medium in the presence of a polyol, and contacting and reacting the resulting polyol-containing vinyl chloride polymer with a non-aromatic polyisocyanate (Unexamined Japanese Patent Publication No. Showa 61-1208
Publication No. 20).

(d) A method of polymerizing a vinyl chloride monomer in the presence of a non-yellowing thermoplastic polyurethane that is soluble in vinyl chloride monomers (Japanese Patent Application Laid-Open No. 48-40312), or A method in which polyol and non-aromatic polyisocyanate are reacted as a solvent, and the non-yellowing produced is subjected to radical polymerization of vinyl chloride monomer in the presence of thermoplastic polyurethane (Japanese Patent Publication No. 53-21038-) A resin composition obtained by.

In the above resin compositions (aJ to Tbl), it is a raw material for non-yellowing thermoplastic polyurethane. Examples of polyols include polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; and polycarbonates such as adipic acid, azelaic acid, sebacic acid etc. Ill ethylene glycol, diethylene glycol, t3- or t4-
Examples include various polyester polyols comprising polyhydroxyl compounds such as butanediol, neopentyl glycol, and t6-hexanediol.

On the other hand, the polyisocyanate, which is another raw material, must be a non-aromatic polyisocyanate, such as tetramethylene diisocyanate, pentamethylene diisocyanate, dimer acid-modified isocyanate, hexamethylene diisocyanate, etc. Aliphatic diisocyanates; alicyclic diisocyanates such as cyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate; and the like.

In addition, a vinyl monomer copolymerizable with the vinyl chloride monomer that can be used together with the vinyl chloride monomer in the formation of the vinyl chloride polymer in the resin composition broadly classified into (a1 to (dl)) Examples include vinylidene monomers such as vinylidene chloride and vinylidene fluoride, vinyl esters such as vinyl acetate, vinyl ethers such as n-7' methyl vinyl ether, imbutyl vinyl ether, and cetyl vinyl ether, olefins such as ethylene, and acrylic fluoride. Acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, cyanoethyl lylate, esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene and styrene derivatives such as methylstyrene, vinyltoluene, and chlorostyrene, vinyl monomers such as acrylonitrile, ethylvinylbenzene, and vinylnaphthalene, and dialkene monomers such as butadiene, isoprene, and chloroprene.

The amount of the copolymerizable vinyl monomer used is preferably 50% by weight or less, more preferably 30% by weight or less, based on the vinyl chloride monomer.

This is because if the amount exceeds 50% by weight, the processability, heat resistance, etc. of the vinyl chloride polymer obtained will deteriorate.

In the resin component of the resin composition of the present invention, the above two types of resins are present as homogeneously as possible in order to achieve well-balanced physical properties such as abrasion resistance, low-temperature properties, oil resistance, and processability. In this respect, the non-yellowing thermoplastic polyurethane and the vinyl chloride polymer are chemically bonded (cl and (d)).
) are preferred, and resin compositions classified as ldl are more preferred.

The hardness of the resin composition in the present invention is 7 in JISA hardness.
A suitable hardness is 0 to 95 (A), and resin compositions with such hardness cannot be generalized because they vary depending on the type of vinyl chloride polymer and non-yellowing thermoplastic polyurethane, but usually The content ratio of the vinyl chloride polymer and the non-yellowing thermoplastic polyurethane in the resin composition is a weight ratio of -゛-Middle (vinyl chloride polymer): (non-yellowing thermoplastic polyurethane) =
(50-70): (50-30) By blending both resins of 5IC1, or adding vinyl chloride monomer to non-yellowing thermoplastic polyurethane and polymerizing it, vinyl chloride monomer can be added. It can be produced by blending a polyol and a polyisocyanate with a combination to form a polyurethane.

Automotive decorations or protective equipment such as moldings molded from the resin composition of the present invention are capable of suppressing changes over time in the color tone of the surface of the molded product and changes over time in the hardness of the molded product, regardless of the hardness of the resin composition. Since the present invention can reduce the JIS A hardness of 70 to 70, the discoloration and change in hardness over time have been particularly noticeable in the past.
It is effective for moldings with iron cores made of soft resin such as 75%.

As an example of the method for producing the resin component in the resin composition of the present invention, a method for producing the resin composition classified as Td), which is particularly preferably used in the present invention, is shown below.

For example, 40 parts by weight of a thermoplastic polyurethane soluble in vinyl chloride monomer and having a softening point of 30 to 60°C as measured by a Koka type flow tester such as Bandex T-5265, T-525 or T-7170. In the presence of ~100 parts by weight, 100 parts by weight of a vinyl chloride monomer is initiated in an aqueous medium using a known suspending agent such as partially saponified polyvinyl alcohol and a known oil-soluble polymerization such as azobisisovaleronitrile. It can be produced by carrying out suspension polymerization with stirring at a polymerization temperature of 40 to 60°C.

The pigment used in the present invention is preferably a pigment for polyvinyl chloride, specifically titanium oxide (white),
Inorganic pigments such as aluminum powder (silver), yellow lead (yellow), chromium 20 (yellow), and navy blue (blue), as well as benzidine yellow (yellow) and tartrazine yellow (yellow)
, benzidine orange (orange) and copper phthalocyanine blue (blue).

In the present invention, for example, the amount of white pigment used to obtain a white molded product is 10% of the resin component in the resin composition.
Generally, it is appropriate that the amount is 10 parts by weight or more per 100 parts by weight of the white pigment and about 10 parts by weight of the red pigment per 100 parts by weight of the resin component in order to obtain a pastel colored molded product, which is a type of cream color. It is appropriate to use 0.5 to 1 part by weight of the pigment, and in order to obtain a silver molded product, it is appropriate to use 5 to 7 parts by weight of the silver pigment per 100 parts by weight of the resin component. be.

The resin composition of the present invention may contain appropriate amounts of additives commonly used in the field of polyvinyl chloride processing, such as stabilizers, fillers, flame retardants, lubricants, ultraviolet absorbing plasticizers, etc. can.

The automotive decoration or protective material of the present invention can be prepared by processing the resin composition using a processing method generally employed in the field of polyvinyl chloride processing, such as extrusion molding or injection molding at a molding temperature of 170 to 180°C. It can be molded by

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, on each side, "part" means part by weight, and "change in color over time" and "change in hardness over time" means those measured by the following methods.

O Create a sheet of 50XIQQ■ with a thickness of 1■ that changes color over time, and
B7753 (using a Sunshine carbon arc lamp type weathering tester), a 2000 hour weathering test was conducted with a cycle of spraying water for 18 minutes every 120 minutes, and the color difference between the sheet surface before and after the test was measured using a color difference meter (Japanese). Measured using Denshoku Kogyo ■).

O Change in hardness over time The hardness of the sheet was measured before and after the same weathering test as in the above-mentioned change in color over time using a JIS K6301 spring-type hardness tester type A.

Example 1 Using a resin composition having the composition shown below, a white belt-shaped sheet having a thickness of 1-1 mm was molded by extrusion molding at a molding temperature of 170°C. The hardness of this sheet was 75 ■.

〔composition〕

Aron NP6000 100 parts Barium stearate 1.5 parts Calcium stearate O, S parts Ultraviolet absorber
0.1 part Montanic acid wax 0.
5 parts Tybake CR80 (trade name, titanium oxide white pigment manufactured by Ishihara Sangyo ■) 10 parts Example 2 In place of the white pigment Tybake CR80 in Example 1, Vinyl Toner Color 80115 (trade name, Dainichiseika Chemical Industry ■) was used as a pigment. The same procedure as in Example 1 was carried out except that 5 parts of silver metallic pigment) was used, and the hardness was 75.
A sheet (A) was obtained.

Example 3 Instead of Aron NP6000 in Example 1, DOM
INAS K700C (Product name, Toyo Soda Chemical Industry ■
All other procedures were the same as in Example 1 except that a hardness of 7? ) A sheet of (A) was obtained.

Example 4 100 parts of polyvinyl chloride with a degree of polymerization of 1.100, 80 parts of adipic acid polyester polyol with a number average molecular weight of 2,000 and a hydroxyl value of 56, and Tybake CR80
10 parts of calcium-zinc composite stabilizer, 0.1 part of ultraviolet absorber, 0.5 part of montanic acid wax, and 10.5 parts of hydrogenated diphenylmethane diisocyanate, and mixed with Henschel mixer at 110°C. The mixture was stirred at high speed for 10 minutes, and then kept on fire for 6 hours at 80°C to complete the urethanization reaction (a compound was obtained). Hereinafter, Example 1
In the same manner as above, a sheet having a hardness of 77 (A) was obtained.

Example 5 For 100 parts of polyvinyl chloride with a degree of polymerization of 1.100,
80 parts of thermoplastic polyurethane pandex T-7170 (trade name, manufactured by Dainippon Ink & Chemicals), Tybake C
10 parts of R80, 1.5 parts of barium stearate, 0.5 parts of zinc stearate, 0.1 part of ultraviolet absorber, and 0.5 parts of montanic acid wax were mixed at high speed in a Henschel mixer at 50°C for 10 minutes, and the mixture was compacted. Got Rand.

Thereafter, in the same manner as in Example 1, a sheet with a hardness of 75 (Al) was obtained.

Comparative Example 1 For 100 parts of polyvinyl chloride with a degree of polymerization of 1.100,
75 parts of dioctyl phthalate, Tybake CR8010
part, barium stearate 1.5 part, zinc stearate 0.5 part, ultraviolet absorber 0.1 part and montanic acid type 7
, 210.5 parts and heated at 60℃ using a Henschel mixer.
A compound was obtained by stirring at high speed for 10 minutes.

Thereafter, in the same manner as in Example 1, a sheet with a hardness of 75 (A) was obtained.

Comparative Example 2 A hardness of 75 was obtained in the same manner as in Comparative Example 1, except that 155 parts of the same silver metallic, phosphorescent pigment vinyl toner color 801 used in Example 2 was used in place of Tie Bake CR80 in Comparative Example 1. A sheet (A) was obtained.

For each of the sheets obtained in Examples 1 to 5 and Comparative Examples 1 to 2 above, the measurement results regarding the change in color over time and the change in hardness over time are shown in Table 1.

Table 1 From Table 1, it can be seen that in the molded product of the present invention, there is little discoloration of the surface color over time, that is, the color and luster immediately after production of the molded product can be maintained for a long period of time, and the hardness changes over time. It turns out that there are few.

Comparative Example 3 All procedures were carried out except that in place of Aron NP6000 in Example 1, a graft polymer obtained by radical polymerization of vinyl chloride monomer in an aqueous medium in the presence of an ethylene-vinyl acetate copolymer was used. A white sheet was obtained in the same manner as in Example 1, but its hardness was too high at 98 (A) and its flexibility was insufficient, making it unsuitable for applications such as molding.

(C) Effects of the Invention The automotive decoration or protective material of the present invention has the following advantages: Even if it is used outdoors for a long period of time, the color tone of the colored coating film on its surface shows very little change over time, and the hardness of the material changes little over time. It has much better physical properties than conventional moldings, etc., and is extremely useful industrially.

Claims (1)

[Claims] 1. A vinyl chloride polymer obtained from a monomer mixture of vinyl chloride monomer or vinyl chloride monomer and a vinyl monomer copolymerizable with it, and chemically bonded or bonded thereto. A decorative or protective material for an automobile, which is formed by molding a resin composition comprising a non-yellowing thermoplastic polyurethane and a pigment.