JP3179642B2 - Vinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a vinyl chloride resin composition, and more particularly, to a vinyl chloride resin composition suitable for an automobile exterior member for coating.

[0002]

2. Description of the Related Art In many cases, vinyl chloride resin compositions which have been used for automotive parts for painting contain plasticizers such as phthalate esters, trimellitate esters and polyesters in many cases. .

However, when a low molecular weight plasticizer such as a phthalate ester is used in a vinyl chloride resin composition, the discoloration of the coating film due to bleeding or migration of the plasticizer into the coating film when coated is caused. , Cross-down, cracks, etc.

[0004] In addition, even when a plasticizer having relatively low migration such as a high-molecular weight plasticizer is used among the trimellitate esters, improvement is not seen as compared with the case where a phthalate ester plasticizer is used. However, the effect of bleeding and transfer to the coating film cannot be ignored.

In a polyester plasticizer, for example, 1,2-butanediol and 1,3-butanediol are usually used as alcohol components.
Butanediol, 1,4-butanediol, hexamethylene glycol, neopentyl glycol, propylene glycol and the like are used in combination. However, with such a polyester plasticizer, migration is improved as compared with the case where a phthalate plasticizer is used, but a satisfactory result in terms of weather resistance has not been obtained.

[0006]

Accordingly, an object of the present invention is to provide a vinyl chloride resin composition having excellent weather resistance and coating properties.

[0007]

Means for Solving the Problems The present inventors have found that the above object can be achieved by blending a polyester plasticizer having a specified type and ratio of a polyhydric alcohol component into a vinyl chloride resin. Completed the invention.

That is, the present invention relates to a vinyl chloride resin composition containing (B) 15 to 200 parts by weight of a polyester plasticizer per 100 parts by weight of the vinyl chloride resin (A). 40% by weight of 1,4-butanediol as a polyhydric alcohol component in the agent
Above, and the and automobile exterior members composition for coating the total amount of neopentyl glycol and propylene glycol is characterized in that 30 wt% or less (however, flop
(Excluding the lastisol composition ).

In the present invention, the amount of 1,4-butanediol is specified to be a certain amount or more as described above, and at the same time, the amounts of neopentyl glycol and propylene glycol are suppressed to a certain amount or less as described above. There are features. Thereby, desired weather resistance and paintability are obtained. Such an effect cannot be obtained only by specifying either one.

The vinyl chloride resin used in the composition of the present invention is not particularly limited, and various known resins can be used. Examples of the vinyl chloride resin include, in addition to a vinyl chloride homopolymer, a copolymer of vinyl chloride with a copolymerizable compound such as ethylene, acrylic acid, methacrylic acid, and an alkyl (meth) acrylate ester; It also includes vinyl chloride copolymerized with an unsaturated monomer having a functional group such as an ester group or an epoxy group.

From the viewpoint of the physical properties and processability of the composition, these vinyl chloride resins have an average degree of polymerization of 400 to 10
It is preferable to use those having a molecular weight of about 000, especially about 600 to 2500.

The polyester plasticizer used as the component (B) contains 1,4-butanediol as a polyhydric alcohol component in an amount of 40% by weight or more, preferably 60% by weight or more, particularly 70% by weight or more. In addition, the total amount of neopentyl glycol and propylene glycol is 30% by weight or less. If 1,4-butanediol is less than 40% by weight, the effects of the present invention, that is, the coating properties and weather resistance are impaired, and if the total amount of neopentyl glycol and propylene glycol exceeds 30% by weight, the gloss of the coating film decreases. . As the polyhydric alcohol component, in addition to the above, polyhydric alcohols usually used in polyester plasticizers, for example, diols such as 1,2-butanediol, 1,3-butanediol, hexamethylene glycol, and glycerin And the like. These can be used alone or in combination. For example, 1,3-butanediol has an effect of improving the preservability of a polyester plasticizer, but if its use amount exceeds 15% by weight, the effect of the present invention is adversely affected, which is not preferable.

As a preferred polyhydric alcohol component, for example, when only 1,4-butanediol (100% by weight) is used, 40 to 100% by weight of 1,4-butanediol and 0 to 30% by weight of neopentyl glycol are used. This is the case of the combination.

The acid component in the polyester plasticizer is not particularly limited, and an acid component usually used in the polyester plasticizer, for example, adipic acid,
Dibasic acids such as azelaic acid and sebacic acid, and polybasic acids such as trimellitic acid can be used. These acids may be used alone or in combination of two or more.

The molecular weight of the polyester plasticizer is 1000
~ 15000, especially about 2000-8000. When the molecular weight is less than 1,000, the migration property and the aging property are inferior, and when it exceeds 15,000, the viscosity of the plasticizer becomes extremely high, so that the compatibility with the vinyl chloride resin tends to deteriorate.

The polyester plasticizer (B) described above comprises:
It can be produced by dehydrating and condensing an alcohol component and an acid component. At that time, a stopper can be used to control the degree of polymerization (or molecular weight).

The above-mentioned (B) polyester plasticizer is
(A) 15 to 200 parts by weight, preferably 20 to 120 parts by weight, based on 100 parts by weight. If the amount of the component (B) is less than 15 parts by weight, the physical properties of the composition, particularly cold resistance, will be poor. If it exceeds 200 parts by weight, the gelation of the composition will be remarkably deteriorated, and the productivity will be reduced.

The resin composition of the present invention may contain, as optional components, an ultraviolet absorber, a light stabilizer, a weathering aid and the like.

As the ultraviolet absorber, a benzotriazole-based, benzophenone-based, salicylic acid derivative, or oxalic anilide derivative may be used alone or in combination of two or more. Particularly, a benzotriazole-based and benzophenone-based ultraviolet absorber is used alone or in combination.

As the light stabilizer, a hindered amine-based or benzoic acid light derivative alone or a mixture of two or more kinds can be used. Particularly preferred are hindered amine light stabilizers.

As the weathering aid, a weathering aid prepared by using an organic phosphate such as aryl phosphite, alkyl phosphite, or alkyl aryl phosphite singly or as a mixture of two or more kinds can be used. Preferably, it is an aryl phosphite.

The amounts of these ultraviolet absorbers, light stabilizers and weathering aids vary depending on the properties of the desired composition, but generally the total amount of component (A) and component (B) is 100.
The amount is preferably 0.1 to 5.0 parts by weight, more preferably 0.1 to 3.0 parts by weight based on parts by weight.

Further, if necessary, a stabilizer, a stabilizing aid,
Fillers, processing aids, flame retardants, lubricants and the like can be mixed. The stabilizer mentioned here includes a heat stabilizer, a discoloration inhibitor, a heat aging inhibitor and the like. There are no particular restrictions on the types of these stabilizers and stabilizing aids, and stabilizers and stabilizing aids commonly used in vinyl chloride resins can be used. Examples of stabilizers include lead-based stabilizers such as tribasic lead sulfate, dibasic lead stearate, dibasic lead phosphite, dibasic lead sulfite, tribasic lead maleate and dibasic phthalic acid. lead, tin-based stabilizers, for example the general formula R _x -Sn-Y
_4-x (R represents an alkyl group such as a methyl group, a butyl group, and an octyl group; Y represents a functional group such as a mercapto group, a maleate group and a carboxyl group; and x represents 1 or 2). Tin compounds, and fatty acid metal salts such as stearic acid, sebacic acid, oleic acid, as fatty acid components,
Such as undecylenic acid and ricinoleic acid, saturated or unsaturated fatty acids of C ₆ -C ₃₄ substituted or unsubstituted lead, zinc,
Salts such as cadmium, magnesium, aluminum, calcium, barium, strontium and the like can be mentioned, but are not limited thereto.

Examples of stabilizing aids include phosphite stabilizing aids such as alkylaryl phosphites, polyhydric alcohol stabilizing aids such as pentaerythritol and dipentaerythritol, β-diketo compounds, fatty acids such as And stearic acid.

As fillers, calcium carbonate, clay,
Talc, mica, wollastonite and the like can be used.

In addition, auxiliary agents such as processing aids, flame retardants, and lubricants can be used to add functions such as workability, surface properties, and flame retardancy.

These stabilizers and auxiliaries are not limited to those described above, and any of those usually used for vinyl chloride resin compositions can be used.

The method for producing the resin composition of the present invention is not particularly limited. Each component of the composition is substantially uniformly dispersed, mixed,
Any manufacturing method can be adopted as long as it is a method of kneading. For example, the composition after dry or hot blending with a Hensyl mixer, a ribbon blender, a tumbler mixer or the like can be directly molded. Also, an extruder such as a Banbury-mixer type, a co-kneader type, a two-axis co-directional type, After melting and kneading with a biaxially different direction type, a stone mill type or the like, it can be formed into a pellet and molded.

The resin composition of the present invention can be further molded by any molding method. For example, it can be selected from methods such as extrusion molding, injection molding, blow molding, calendar molding, and vacuum molding according to the desired product.

The resin composition of the present invention is suitable for coating applications. A known method can be used as the coating method. As the paint to be used, polyester urethane-based, acrylic urethane-based, and acrylic melamine-based paints can be used, but polyester urethane-based and acrylic urethane-based paints are preferred. When weather resistance is required, acrylic urethane is preferred.

As the composition of the paint layer, a composition such as a primer paint layer on a resin layer and an overcoat paint layer thereon is desirable. The primer coating layer improves the adhesion between the top coating layer and the resin composition, and also has the effect of suppressing the migration of the plasticizer contained in the resin composition. The thickness of the primer coating layer is preferably from 5 to 35 μm. More preferably, it is 10 to 30 μm. The thickness of the top coat layer is
10 to 100 μm is preferred. More preferably, 25
60 μm.

The following examples further illustrate the present invention.

[0033]

Examples 1 to 6 and Comparative Examples 1 to 7 The following Table 1 is based on 100 parts by weight of vinyl chloride resin (hereinafter sometimes referred to as PVC, TH-1300 manufactured by Tosoh Corporation, degree of polymerization 1300). The polyester plasticizers A to M shown in
5 parts by weight, epoxidized oil (manufactured by Asahi Denka Kogyo KK, O-
130S) 5 parts by weight, Ba-Zn-based stabilizer (Rup-14, manufactured by Asahi Denka Kogyo Co., Ltd.) 3 parts by weight, UV absorber (benzotriazole-based, Ciba Geigy Co., Ltd., Tinuvin P) 0.5 part by weight, 0.3 parts by weight of light stabilizer (hindered amine, LA-62 manufactured by Asahi Denka Kogyo Co., Ltd.), heavy calcium carbonate (Nitto Powder Chemical Co., Ltd., N
S-400) 50 parts by weight, a total of 2 parts by weight of carbon black (manufactured by Dainichi Seika Co., Ltd., K-115) and titanium oxide (manufactured by Dainichi Seika Co., Ltd., E-180) as colorants, uniformly. Mix and disperse to make a formulation.

The following compound was kneaded with an 8-inch roll manufactured by Kansai Roll Co., Ltd. at a kneading temperature of 150 ° C. for 5 minutes to obtain a kneaded material.

The obtained kneaded material was preheated at a temperature of 180 ° C. for 2 minutes using a hot press machine manufactured by Kansai Roll Co., Ltd.
/ Cm 2 for 2 minutes and pressed into a uniform 3 mm thick sheet.

The obtained sheet is placed in a predetermined (130 mm × 16
0 mm), the surface was degreased by wiping with isopropyl alcohol (IPA), and then left at room temperature for 48 hours. -278)
Is applied with an air spray gun to a thickness of 15 to 25 μm, and a base coat layer of an acrylic urethane-based paint (R-255, manufactured by Nippon Bee Chemical Co., Ltd.)
Is applied with an air spray gun so as to have a thickness of 10 to 15 μm, and a clear coat layer (R-266, manufactured by Nippon Bee Chemical Co., Ltd.) is coated thereon with a thickness of 25 to 30 μm.
After applying with an air spray gun to become
It baked and dried over 30-45 minutes at 30 degreeC.

The paintability of the molded product was visually observed, and a good product was evaluated as ○, a slightly poor product was evaluated as Δ, and a poor product was evaluated as ×.

Further, the molded article was subjected to a weather resistance test using a sunshine carbon weather meter according to the 7.6 accelerated weather test method of JIS D 0205, and sampled every 500 hours up to 2000 hours. Gloss (gloss change) of the sampled sample with a color difference meter, a gloss meter (Nippon Denshoku Co., Ltd.) and an optical microscope.
The comparison was made as to whether there was no color change, whether there was a color change, or whether cracks occurred in the surface state of the test piece. Very good ones were evaluated as ◎, good ones as ○, slightly poor ones as △, bad ones as ×, and very poor ones as XX.

Table 2 shows the results of the above test.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

Example 7 65 parts by weight of a polyester plasticizer A shown in Table 1 was added to 100 parts by weight of a vinyl chloride resin (TH-1300 manufactured by PVC Tosoh Corporation, degree of polymerization: 1300), and an epoxidized oil (Asahi Denka Industrial Co., Ltd., O-130
S) 5 parts by weight, 3 parts by weight of Ba-Zn-based stabilizer (Rup-14, manufactured by Asahi Denka Kogyo Co., Ltd.), 0.5 parts by weight of an ultraviolet absorber (benzotriazole-based, Ciba Geigy, Tinuvin P), 50 parts by weight of heavy calcium carbonate (NS-400, manufactured by Nitto Powder Chemical Co., Ltd.), and carbon black (K-1 manufactured by Dainichi Seika Co., Ltd.) as a coloring agent
15) and titanium oxide (E-18, manufactured by Dainichi Seika Co., Ltd.)
0) and a total of 2 parts by weight were uniformly mixed and dispersed to prepare a blend.

Next, a resin composition was produced in the same manner as in Example 1, then subjected to compression processing to form a sheet, and a paint was applied thereto, and subjected to various tests similar to those in Example 1.
Table 3 shows the results.

[0044]

Comparative Example 8 Example 7 was repeated except that the polyester plasticizer I shown in Table 1 was used in place of the polyester plasticizer A.
A composition similar to the above was produced.

Next, this resin composition was subjected to compression processing in the same manner as in Example 1 to form a sheet, and a coating material was applied thereto, and subjected to various tests similar to those in Example 1. Table 3 shows the results
Shown in

[0046]

Example 8 65 parts by weight of a polyester plasticizer A shown in Table 1 was added to 100 parts by weight of a vinyl chloride resin (TH-1300 manufactured by PVC Tosoh Corporation, degree of polymerization: 1300), and an epoxidized oil (Asahi Denka Industrial Co., Ltd., O-130
S) 5 parts by weight, 3 parts by weight of Ba-Zn based stabilizer (Rup-14, manufactured by Asahi Denka Kogyo Co., Ltd.), 0.5 parts by weight of ultraviolet absorber (benzophenone type, 143, manufactured by Asahi Denka Kogyo Co., Ltd.) Heavy calcium carbonate (manufactured by Nitto Powder Chemical Co., Ltd.
NS-400) 50 parts by weight, and carbon black (K-115, manufactured by Dainichi Seika Co., Ltd.) and titanium oxide (E-180, manufactured by Dainichi Seika Co., Ltd.) as colorants in total of 2 parts.
The parts by weight were uniformly mixed and dispersed to prepare a blend.

Next, a resin composition was produced in the same manner as in Example 1, and then subjected to compression processing to form a sheet, and a coating material was applied thereto, and subjected to various tests similar to those in Example 1.
Table 3 shows the results.

[0048]

Example 9 65 parts by weight of a polyester plasticizer A shown in Table 1 was added to 100 parts by weight of a vinyl chloride resin (TH-1300 manufactured by PVC Tosoh Corporation, degree of polymerization: 1300), and an epoxidized oil (Asahi Denka) Industrial Co., Ltd., O-130
S) 5 parts by weight, Ba-Zn-based stabilizer (Rup-14, manufactured by Asahi Denka Kogyo Co., Ltd.), 3 parts by weight, ultraviolet absorber (benzotriazole-based Ciba Geigy, Tinuvin P)
0.5 parts by weight, 0.5 parts by weight of an organic phosphoric acid ester (manufactured by Asahi Denka Kogyo KK, Mark 1500) as a weathering aid,
Heavy calcium carbonate (NS-
400) 50 parts by weight, and a total of 2 parts by weight of carbon black (K-115, manufactured by Dainichi Seika Co., Ltd.) and titanium oxide (E-180, manufactured by Dainichi Seika Co., Ltd.) as colorants, uniformly mixed Dispersed to make a formulation.

Next, a resin composition was produced in the same manner as in Example 1, then subjected to compression processing to form a sheet, and a coating material was applied thereto, and subjected to the same various tests as in Example 1.
Table 3 shows the results.

[0050]

Comparative Example 9 Example 9 was repeated except that the polyester plasticizer I shown in Table 1 was used in place of the polyester plasticizer A.
A composition similar to the above was produced.

Next, this resin composition was subjected to compression processing in the same manner as in Example 1 to form a sheet, and a coating material was applied thereto, and subjected to various tests similar to those in Example 1. Table 3 shows the results
Shown in

[0052]

[Table 3]

[0053]

According to the present invention, it is possible to provide a vinyl chloride resin composition having excellent weather resistance and coatability.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takayuki Onda 1-4-1 Chuo, Wako-shi, Saitama Prefecture Inside of Honda R & D Co., Ltd. (72) Katsuo Miyazaki 1-4-1 Chuo, Wako-shi, Saitama Stock Inside the Honda R & D Co., Ltd. (72) Inventor Tatsuya Itakura 1-4-1, Chuo, Wako-shi, Saitama Stock Company Inside the Honda R & D Co., Ltd. (56) References JP-A-63-99226 (JP, A) JP-A-2-155942 (JP, A) JP-A-7-53909 (JP, A) JP-A-7-48494 (JP, A A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 27/06 C08L 67/00-67/08

Claims (1)

(57) [Claims] 1. A (B) vinyl chloride resin composition containing 15 to 200 parts by weight of a polyester plasticizer with respect to 100 parts by weight of a vinyl chloride resin. As a dihydric alcohol component,
1,4-butanediol is 40% by weight or more, and the total amount of neopentyl glycol and propylene glycol is 30% by weight or less for coating.
Composition for automotive exterior parts ( however, plastisol composition
Except for).