JPH10130566A - Plastisol composition of vinyl chloride-based resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a plastisol composition of a vinyl chloride-based resin, capable of sufficiently curing and solidifying at 110-180 deg.C, extremely slight in volatile component in heating, excellent in coating workability, retaining good storage stability and excellent in chipping resistance. SOLUTION: This plastisol composition is composed of a vinyl chloride-based resin, a plasticizer and a filler. The plasticizer comprises is obtained by mixing a 19-23C dibasic ester-based plasticizer (A) with 19-24C monobasic ester-based plasticizer (B) in a weight ratio of (5/1) to (1/5) and an amount of the plasticizer mixture used is 80-200 pts.wt. based on 100 pts.wt. vinyl chloride-based resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin plastisol composition, and more particularly, to a composition which is sufficiently cured or solidified in a heating temperature range of 110 to 180.degree. Is very low)
Moreover, it is excellent in coating workability, and has excellent storage stability and excellent chipping resistance. For example, a sealant between body panels in a car production line, a paint on a panel surface, or a rust preventive paint on a vehicle floor floor ( And a plastisol composition useful as an undercoat).

[0002]

2. Description of the Related Art In general, a vinyl chloride resin plastisol composition is obtained by mixing and dispersing a vinyl chloride resin together with a filler and other compounding agents in a plasticizer. It is used as a sealant in between, a paint on the panel surface, or a rust preventive paint (undercoat) on the floor behind the vehicle. By the way, an important issue in an automobile production line is to improve the working environment. Among them, it is desired to reduce volatile components (particularly, volatilization of organic material components) which affect the human body and the global environment. For example, a "solvent-free plastisol composition comprising a specific vinyl chloride copolymer, an inorganic filler and a plasticizer" is known.
Gel bonding is possible even at low temperatures, and the adhesive strength is high,
In addition, it has good viscosity stability over time (see Japanese Patent Application Laid-Open No. 4-142380), but these effects are obtained by using a specific vinyl chloride copolymer as vinyl chloride 60-96.
This is due to the use of a copolymer of a carboxylate vinyl ester and a monoalkyl maleate by weight, and is not directly related to the use of a plasticizer.

[0003] On the other hand, the above-mentioned undercoat uses require excellent coating workability (low viscosity), good storage stability (viscosity stability over time), and excellent chipping resistance. For example, Japanese Patent Application Laid-Open No. 4-81477 discloses a chipping-resistant coating for undercoating, which includes "vinyl chloride / vinyl acetate copolymer, plasticizer, inorganic filler,
A plastisol composition comprising an organic filler (hollow resin powder) and an adhesion-imparting agent, wherein the plasticizer is a phthalic acid ester alone or an aliphatic dibasic acid ester added thereto is disclosed. However, when such a plasticizer is used, there is a problem in dischargeability in spray coating, and the coating operation has not been improved.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to
Fully cured or solidified in a heating temperature range of 0 to 180 ° C.,
In addition, it has a very small amount of volatile components during the heating (hereinafter referred to as low volatility), has excellent coating workability, maintains good storage stability, and has excellent chipping resistance in undercoat applications. An object of the present invention is to provide a vinyl resin plastisol composition.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and found that a dibasic acid having a specific carbon number as a plasticizer was added to a general-purpose vinyl chloride resin and a filler. The inventor has found that if the mixture of the ester and the monobasic acid ester at a specific ratio is blended at a specific ratio, the intended purpose can be completely achieved, and the present invention has been completed. That is, the present invention provides a plastisol composition comprising a vinyl chloride resin, a plasticizer and a filler,
The plasticizer is a dibasic acid ester-based plasticizer (A) having 19 to 23 carbon atoms (C _{19 to 23} , also referred to as the same hereinafter) and C _{19 to 24.}
Of a monobasic ester plasticizer (B) at a weight ratio of 5/1 to 1/5, and the amount of the mixture used is 100 parts by weight of a vinyl chloride resin (parts by weight, the same applies hereinafter). The present invention provides a vinyl chloride resin plastisol composition characterized in that the amount is 80 to 200 parts.

As the vinyl chloride resin used in the present invention, those known per se may be used. For example, (i) vinyl chloride alone or a comonomer copolymerizable with vinyl chloride is emulsifier and water-soluble polymerization initiator A vinyl chloride paste resin having a particle size of 5 μm or less, preferably about 0.05 to 3 μm, which is produced by emulsion polymerization in the presence of: (ii) in the presence of a dispersant and an oil-soluble polymerization initiator,
Examples thereof include those produced by a fine suspension polymerization method in which vinyl chloride alone or a comonomer copolymerizable with vinyl chloride is mechanically finely dispersed and then polymerized. In addition, in addition to these, a relatively large particle-size vinyl chloride resin produced by ordinary suspension polymerization is used in combination within a range that does not adversely affect the viscosity, flowability, processability, etc. of the paste sol. No problem. Examples of the copolymerizable comonomers include vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate; acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate and hydroxyethyl acrylate; methyl methacrylate and ethyl methacrylate And methacrylic esters such as hydroxyethyl methacrylate; maleic esters such as dibutyl maleate and diethyl maleate; fumaric esters such as dibutyl fumarate and diethyl fumarate; vinyl methyl ether, vinyl butyl ether and vinyl octyl ether Vinyl cyanides such as acrylonitrile and methacrylonitrile; ethylene,
Α-olefins such as propylene and styrene; and vinylidene halides such as vinylidene chloride and vinyl bromide and other vinyl halides. One or a mixture of two or more of these may be used in an amount of 30% of the total monomers.
(% By weight, the same applies hereinafter), and preferably in the range of 20% or less.

As the plasticizer in the present invention, the above C
_19-23 dibasic acid ester plasticizer (A) (hereinafter simply referred to as plasticizer (A)) and C _19-24 monobasic acid ester plasticizer (B) (hereinafter simply plasticizer (B)) ). In addition, such a plasticizer (A), (B)
If each is less than C ₁₉ , the volatile components tend to increase during heating, and if each exceeds the upper limit of the carbon number, the coating workability will decrease due to an increase in viscosity.

The plasticizer (A) has a general formula: [Wherein, R ₁ , R ₂ and R ₃ are each a saturated or unsaturated hydrocarbon group selected from aliphatic, alicyclic and aromatic (provided that R ₁ is divalent and R ₂ and R ₃ are Monovalent)]
And those of C _19-23 are included, for example, C
₁₉ dipentyl azelate; C ₂₀ diheptyl adipate, dipentyl sebacate, dihexyl phthalate, butyl octyl phthalate; C ₂₁ dihexyl azelate; C ₂₂ dihexyl sebacate, diheptyl phthalate, dioctyl adipate and the like. And one or a mixture of two or more of these.

The plasticizer (B) has a general formula: Wherein R ₄ and R ₅ are each a saturated or unsaturated monovalent hydrocarbon group selected from aliphatic, alicyclic and aromatic, and include those having C _19-24. is, for example, methyl oleate C _19, methyl stearate, ethyl oleate C _20, butyl palmitate,
Hexyl myristate, octyl laurate, 2-ethylhexyl laurate, capric caprylic; C ₂₁ isopropyl oleate, n- propyl, pentyl palmitate, Misuchin acid pentyl, lauric acid isononyl; of C ₂₂ isobutyl oleate, Oleic acid n
- butyl, butyl stearate, hexyl palmitate, Misuchin octyl, Misuchin 2-ethylhexyl, decyl laurate, lauryl caprate, cyclohexyl palmitate, benzyl; palmitate heptyl of C _23, methyl palmitate cyclohexyl; C ₂₄ octyl palmitate, 2-ethylhexyl palmitate and the like, and one or a mixture of two or more thereof is used.

The combination ratio of the plasticizer (A) and the plasticizer (B) is an important factor that can contribute to particularly good storage stability and excellent chipping resistance. / 1 to 1/5. When the plasticizer (A) is used beyond the upper limit of this ratio range, it contributes to the improvement of the coating workability due to the decrease in viscosity. However, since the compatibility with the vinyl chloride resin is good, the plasticizer (A) is used during storage. As a result of the resin tending to swell and increase in viscosity, there is a problem in storage stability. Conversely, when the plasticizer (A) is below the lower limit of the above-mentioned ratio range, that is, when the plasticizer (B) is used beyond the above-mentioned ratio, the compatibility with the vinyl chloride resin is poor, so that the viscosity storage There is no problem with stability,
A decrease in chipping resistance is inevitable.

[0011] The amount of the mixture of the plasticizer (A) and the plasticizer (B) used together in such a predetermined ratio is as follows.
80 to 200 parts, preferably 80 to 100 parts with respect to 00 parts
Select within the range of parts. If the amount is less than 80 parts, the ejection property is reduced due to the increase in viscosity, and if it exceeds 200 parts, the chipping resistance becomes unsatisfactory.

In the present invention, if necessary, a plasticizer (C) having a weight average molecular weight of 250 or more and a boiling point of 250 ° C. or more is used as a third plasticizer other than the plasticizers (A) and (B). It may be used in a proportion of 70% or less of all the plasticizers. When used over 70%, the intended low volatility,
It is expected that coating workability, storage stability, and / or chipping resistance will be adversely affected. Particularly, it is recognized that the coating workability is decreased due to an increase in viscosity. Examples of the plasticizer (C) include di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, diheptyl phthalate, diphenyl phthalate, ditridecyl phthalate, diundecyl phthalate, dinonyl phthalate and the like. Isophthalic acid derivatives such as di-2-ethylhexyl isophthalate and diisooctyl isophthalate; di-2-ethylhexyl tetrahydrophthalate;
Tetrahydrophthalic acid derivatives such as di-n-octyl tetrahydrophthalate and diisodecyl tetrahydrophthalate; adipic acid derivatives such as diisodecyl adipate and diisononyl adipate; maleic acid derivatives such as diisodecyl maleate; fumaric acid derivatives such as diisodecyl fumarate Tri-2-ethylhexyl trimellitate, tri-n-octyl trimellitate, triisodecyl trimellitate, triisooctyl trimellitate;
Trimellitic acid derivatives such as tri-n-hexyl trimellitate and triisononyl trimellitate; tetra-2-ethylhexyl pyromethate, tetra-pyrometate
pyrometic acid derivatives such as n-octyl; citric acid derivatives such as triethyl citrate, acetyltriethyl citrate, acetyltri-2-ethylhexyl citrate; itaconic acid derivatives such as diisodecyl itaconate; glyceryl monooleate and diethylene glycol monooleate Oleic acid derivatives; ricinoleic acid derivatives such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate, diethylene glycol monoricinoleate; glyceryl monostearate;
Stearic acid derivatives such as diethylene glycol distearate; other fatty acid derivatives such as diethylene glycol monolaurate and pentaerythritol fatty acid esters; tributyl phosphate, trihexyl phosphate, tri (2-ethylhexyl) phosphate, octyl diphenyl phosphate, dodecyl diphenyl phosphate, dioctyl Phenyl phosphate, dibutyl phenyl phosphate, tributoxyethyl phosphate,
Phosphate derivatives such as triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (chloroethyl) phosphate; tridecylbenzene, tetradecylbenzene, pentadecylbenzene, hexadecylbenzene,
Heptadecylbenzene, octadecylbenzene, nonadecylbenzene, eicosylbenzene, heneicosylbenzene, docosylbenzene, tricosylbenzene, tetracosylbenzene, pentacosylbenzene, hexacosylbenzene, heptacosylbenzene, octakoshi Alkylbenzenes such as benzene, nonacosylbenzene, and tricontylbenzene; epoxidized soybean oil, epoxybutyl stearate, and epoxyhexahydrophthalic acid di-
Epoxy derivatives such as 2-ethylhexyl, epoxyisodidecyl hexahexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, epoxidized decyl oleate; polyester plasticizers such as adipic acid polyester, sebacic polyester, and phthalic polyester And one or two of these.
Mixtures of more than one species may be used. In particular, _C24-30 phthalic acid derivatives (di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, diundecyl phthalate, etc.) are highly versatile, so that desired performance effects can be maintained. This contributes to a reduction in material costs.

The filler used in the present invention includes, for example, surface-treated calcium carbonate, heavy calcium carbonate, talc, clay, barium sulfate, alumina, silica and the like. One or a mixture of two or more of these can be used. I do. The amount used is usually 3 parts per 100 parts of the vinyl chloride resin.
The selection may be made in the range of 0 to 350 parts, preferably 50 to 250 parts. If the amount is less than 30 parts, the relationship between the viscosity and the physical properties becomes worse, and there is a tendency not to contribute to the reduction of the material cost.
If it exceeds 350 parts, the coating workability and chipping resistance tend to decrease.

Further, in addition to the above-mentioned filler, a usual hollow substance may be added as required, for example, for the purpose of weight reduction. Examples of such a hollow material include amino resin, phenol resin, polyester resin, polyolefin resin, acrylonitrile resin, silicone resin, vinylidene chloride / acrylonitrile copolymer resin, acrylonitrile / isobornyl methacrylate copolymer resin, acrylonitrile / isobornyl acrylate An organic resin such as a copolymer resin; or an inorganic resin such as glass, shirasu, fly ash, silica, alumina, or carbon.
Mixtures of more than one species may be used. Usually, it is appropriate to select the amount to be used in the range of 0.3 to 10% of the total amount of the composition. If it is less than 0.3%, the effect of lowering the specific gravity is low, and the desired weight reduction cannot be obtained. If it exceeds 10%, the physical properties tend to be impaired.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride resin plastisol composition according to the present invention comprises the above-mentioned vinyl chloride resin in a predetermined ratio; plasticizers (A) and (B), and optionally a plasticizer (C). And a system in which a filler and, in addition, if necessary, a hollow substance are blended and uniformly dispersed and mixed, and if necessary, a usual additive component, for example, an adhesion-imparting agent [dimer acid, resin acid, Monoamide or polyamide compound obtained by reacting a polymerized fatty acid or the like with a polyamine; epoxy resin, acrylic resin, phenol resin, blocked isocyanate compound (in this case, a dissociation accelerator for dissociation of a blocking agent can be used in combination) , Mercapto compounds, etc.), thixotropic agents (fine powdered silica, organic bentonite, etc.), colorants (titanium oxide, carbon black, dyes and pigments, etc.), moisture absorbents (Ca O, Al ₂ O ₃ , CaCl _2, etc.) may be added in an appropriate amount.

[0016]

Next, the present invention will be described more specifically with reference to examples and comparative examples. Examples 1 to 6 and Comparative Examples 1 to 5 (1) Preparation of plastisol composition Components of the number shown in the following Table 1 are sequentially put into a mixing and stirring tank, and stirred and mixed for 60 minutes and defoamed.

[Table 1]

[0017] In Table 1, Note 1) Kaneka Co. vinyl chloride paste resin, "PSH-10" Note 2) DHP: diheptyl phthalate DOA of C _22: dioctyl adipate of C ₂₂ Note 3 ) BOL: isobutyl oleate MS of C _22: methyl stearate MOL of C _19: methyl oleate C ₁₉ Note 4) DOP: di-2-ethylhexyl phthalate Note 5 C ₂₄₎ Shiraishi Kogyo Co., Ltd. Surface-treated calcium carbonate, "Shiroyuka CC-R" Note 6) Heavy calcium carbonate manufactured by Shiroishi Calcium Co., Ltd.
"Whiteton B"

(2) Performance test For each plastisol composition prepared in the above (1),
The following four tests were performed, and the results are shown in Table 1. Volatility test 0.5 g of each plastisol composition is weighed on an aluminum foil dish of known weight (however, measured to the nearest 0.1 mg). Next, 3 ml of toluene is added and after sufficient stirring, the aluminum foil dish is heated at 110 ± 5 ° C. for 60 minutes. Cool to 20 ° C. in desiccator and measure to the nearest 0.1 mg. The non-volatile content (%) at this time is calculated by subtracting the sample weight after heating by the sample weight before heating by 1
Determined by multiplying by 00. The larger the nonvolatile content, the smaller the volatile component, that is, the lower the volatility. ○: 99% or more of non-volatile content ×: Less than 99% of non-volatile content

[0019] The test discharge test is a test assuming coated easiness of the plastisol composition, a nozzle 3 mm.phi, length 50 mm, pressure 5kg
・ Calculate the volume (cc) of discharge per minute using a sea bath discharge meter under the condition of f / cm ² . The greater the value of the discharge amount (cc / min) at this time, the better the dischargeability, that is, the better the coating workability. ：: discharge amount (cc / min) 1500 or more Δ: 1000 ≦ discharge amount <1500 ×: discharge amount less than 1000

Storage Stability Test Each plastisol composition was allowed to stand at 20 ° C. for 3 hours, and the viscosity (cps) was measured using a B-type rotary viscometer under the condition of No. 7 rotor at 20 rotations. I do. Separately, 40
Each plastisol composition left for 10 days at 20 ° C.
After 3 hours, the viscosity is measured under the same conditions as above, and this is defined as the viscosity after storage. The value obtained by subtracting the initial viscosity from the viscosity after storage is reduced by the initial viscosity, and the obtained numerical value is multiplied by 100 to obtain a viscosity change rate (%). Those with a small rate of change in viscosity have good storage stability. ：: viscosity change rate less than ± 30% ×: viscosity change rate ± 30% or more

[0021] Chipping resistance test JASO-M-306-88 (Japan Society of Automotive Engineers of Japan,
Abrasion resistance test prescribed in the March 30, 1988 revision, automobile standard, underbody coating): 5-2
Perform according to the 1B method. Evaluated by the total weight (kg) of the nuts dropped before the coating film was broken, the larger the value, the better the chipping resistance. ○: 40 kg or more, ×: less than 40 kg

[0022]

According to the results shown in Table 1, the compositions of the present invention exemplified in Examples 1 to 6 have low volatility and good dischargeability, that is, excellent coating workability and good storage stability. It is recognized that the compound has good chipping resistance as well as excellent properties. On the other hand, in Comparative Example 1 in which the plasticizers (A) and (B) were not used, the coating workability was poor; and in Comparative Example 2 in which a high boiling point solvent was used in order to improve the workability, the volatility was high, and Less volatile. Further, when either one of the plasticizers (A) and (B) is lacking, for example, in Comparative Examples 3 and 4 lacking the plasticizer (B), poor storage stability was observed. Comparative Example 5 lacking A)
, It is recognized that the chipping resistance tends to be poor.

Claims (4)

[Claims] 1. A plastisol composition comprising a vinyl chloride resin, a plasticizer and a filler, wherein the plasticizer comprises:
It consists of mixing a dibasic acid ester plasticizer having 19 to 23 carbon atoms (A) and a monobasic acid ester plasticizer having 19 to 24 carbon atoms (B) in a weight ratio of 5/1 to 1/5. A vinyl chloride resin plastisol composition, wherein the amount of the mixture used is 80 to 200 parts by weight based on 100 parts by weight of the vinyl chloride resin. 2. The amount of the filler used is as follows:
The amount is 30 to 350 parts by weight based on 00 parts by weight.
3. The plastisol composition according to item 1. 3. A ratio of a plasticizer (C) having a weight average molecular weight of 250 or more and a boiling point of 250 ° C. or more as a third plasticizer other than the plasticizers (A) and (B) in a total plasticizer of 70% by weight or less. The plastisol composition according to claim 1 or 2, which is used in (1). 4. The plastisol composition according to claim 3, wherein the plasticizer (C) is a phthalic acid derivative having 24 to 30 carbon atoms.