JPS63264654A - resin molded products - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to plastisol compositions, and more specifically,
Hardness, matteness, and dryness of the clothing surface.

The present invention relates to a plastisol composition capable of producing various molded articles with low tenacity.

(Conventional technology) Planutisol can be molded into a wide range of shapes, from hard to soft, by simply shaping it into a European shape and heating it.
Used for a variety of purposes. Examples include paint, exposed floors, wallpaper, anti-corrosion paint, pre-coated steel plates, gloves, boots, leather, toys, films, adhesives, and wearable items.

The chemical structure and amount of plasticizers greatly affect the hardness and texture of the product, but in sol processing, they serve as a dispersion medium for vinyl chloride polymer particles, so they also have a decisive effect on processability. Naturally, if there is a large amount of plasticizer, the sol will have a low viscosity and will be easier to process. On the other hand, when obtaining a hard product, the amount of plasticizer must be reduced, resulting in poor processability. It has been often pointed out that soft vinyl chloride resin has a sticky feel on the surface, which reduces the product value depending on the application.

Various methods have been tried so far to increase the hardness or eliminate the stickiness of the surface.

Reducing the amount of plasticizer increases the viscosity of the sol, making it difficult to process. Methods using reactive plasticizers such as (meth)acrylic acid esters and diallyl phthalate as part of the plasticizer require a peroxide catalyst during compounding, which poses safety issues and may cause vinyl chloride resin to be released during heating and melting. There are problems such as accelerating splitting and increasing viscosity due to reactive plasticizers starting to polymerize during storage of the sol. The method of reducing the amount of plasticizer and replacing part of the resin for polyvinyl chloride paste with vinyl chloride resin of large particle size has a limit on the amount of plasticizer used, and even coarse particles cannot be used as plasticizer after melting. Since it swells and softens, there is a limit to its ability to increase hardness and prevent stickiness. Furthermore, the method of adding inorganic substances is effective in increasing hardness and improving stickiness, but increasing the viscosity of the sol deteriorates processability and significantly reduces product strength. Furthermore, the method of treating the surface of the product with a different surface using an acrylic polymer or polyurethane requires many steps and is economically disadvantageous.

(Problems to be Solved by the Invention) The present inventors have discovered that by using a specific methacrylate resin and plasticizer in a plastisol composition, it is possible to increase the hardness of the product and improve stickiness without impairing processability. I found the scales easily.

(Means for solving the problem) That is, according to the present invention, in a branched sol composition comprising a, a polyvinyl chloride paste resin, b, a methacrylate resin, and c. a plasticizer, b is methyl methacrylate. A homopolymer or copolymer containing 90% by weight or more of
A branched sol composition is provided, characterized in that the weight ratio of a/b is 20/80 to 9515.

The resin for polyvinyl chloride paste used in the present invention may be any resin as long as it is produced by Emulno 17 polymerization or milk suspension polymerization and can be dispersed in a plasticizer to form a sol. In addition to vinyl chloride homopolymer, Copolymers of vinyl chloride and vinyl acetate, vinyl zolopionate, if[hynylidene chloride, entele acrylate, methacrylate ester, etc.] are used alone or in combination with vinyl chloride monopolymers.

Most paste resins have an average particle size of 0.1 to 2 μm, but a portion of the paste resin can be replaced with a vinyl chloride resin having an average particle size of 10 to 200 μm.

As the methacrylate resin, a homopolymer containing 90 or more methyl methacrylates or a copolymer of methyl methacrylate and another monomer copolymerizable therewith is used. Examples of other monomers include acrylic acid, methyl acrylate, ethyl acrylate, globyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, hydroxyethyl acrylate. , hydroxyethyl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, allyl acrylate-1
・、(Acrylates such as polycoalkylene glycol acrylate, trimethylolpropane triacrylate, acrylic acid metal salts; methacrylic acid, ethyl methacrylate, globyl methacrylate, butyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, methoxyethyl methacrylate, butoxyethyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate,
Methacrylates such as dimethylaminoethyl methacrylate, glycidyl acrylate, allyl methacrylate, (poly)alkylene glycol dimethacrylate, trimethylolpropane trimethacrylate; ethylene,
Olefins such as propylene; didines such as butadiene and isoprene;
Examples include vinyl rhodanide; vinyl esters of vinyl acetate and vinyl gropionate; vinyl ethers of allyl vinyl ether; and styrene derivatives such as styrene and chlorstyrene. If the methacrylate is less than 903 (by weight), the Tg will decrease and it will be difficult to obtain the desired feel.The average molecular weight of the methacrylate resin must be 100,000 or more (the average molecular weight here is determined by liquid chromatography). It was measured with

Weight average molecular weight. same as below. ) If it is less than 100,000, the matting effect is insufficient.

A higher degree of polymerization is preferable, and a crosslinked polymer that is insoluble in a solvent may be used. If the average molecular weight is 100,000 or more, it is effective for hardness and matteness, but if it is 1,000,000 or more, or if it is a crosslinked polymer, even higher effects can be obtained. The methacrylate resin should have an average particle size of 1 micron to 200 micron. If it is less than 1μ, the matting effect will be insufficient, and 200μ
Exceeding this value will actually impair the appearance of the product. Larger particle sizes do not necessarily improve the matte effect, dryness, and dryness, but they produce different effects depending on the particle size. It gives a textured surface, and those with a relatively large particle size give a product with a rough feel. All have excellent matte and dry touch properties. The methacrylate resin (b) is used in combination with the polyvinyl chloride-based H'fl resin (, ), and the weight ratio a/b used must be in the range of 20/80 to 9515. If the nose is less than 20/80,
The strength of the molded product deteriorates, and its value as a product decreases. 9
If it exceeds 515, the matte and dry touch effects will be insufficient.

The plasticizer may be any one commonly used for vinyl chloride resins, such as dibutyl phthalate,
Butyl benzyl 7 tallate, no 2-ethylhexyl 7
7-thalic acid esters such as thalate, diisononyl phthalate, mixed alkyl 7-thalate, diisodecyl phthalate, phosphoric acid esters such as tricresyl phosphate and trioctyl phosphate, dibasic acids such as adipic acid and phthalic acid, ethylene glycol, propylene Polyester plasticizers that are condensates with dihydric alcohols such as glycols, dialkyl fatty acid esters such as nooctyl adibate, dioctyl azelate, and subbutyl sepacate, chlorinated paraffins, and epoxidized vegetable oils can be used. The plasticizer swells the vinyl chloride resin at high temperatures, softens and dissolves the particles, and homogenizes them to form a homogeneous FA.

The objectives of the present invention to improve hardness, mattness, dryness, and hardness are: 1. Adding microscopic irregularities to the product surface, 2. Including hard particles in the system, 2. Resin JgJ that is not plasticized on the surface. This is thought to be achieved by a mechanism such as formation of a plasticizer, but this is inconsistent with the above-mentioned mechanism in which a plasticizer dissolves the resin. However, the composition of the present invention resolves this contradiction. In other words, methacrylate resin has a slower absorption rate of plasticizer than polyvinyl chloride, but its absorption capacity is also low, and even if it absorbs plasticizer, its melt viscosity is very high, so polyvinyl chloride is heated and melted. However, methacrylate resin is difficult to melt and flow, so the surface is not smoothed due to surface tension and tends to remain uneven.Also, there is little plasticizer inside and on the surface of the methacrylate resin that appears on the surface, making it sticky. It is thought that the hardness and surface dry touch properties are improved by such a mechanism that there are few substances that cause this, and the degree of plasticization of the 1 methacrylate resin is small, and the hardness is high even when cooled to room temperature. As a methacrylate resin, it has a high average degree of polymerization,
The higher the methyl methacrylate content, the more difficult it is to melt and flow, and the greater the effect.

In addition, methacrylate resin is compatible with polyvinyl chloride, so after melt molding, the polymer at the particle interface becomes uniformly compatible, resulting in no loss of mechanical or physical properties. You can get a strong product. Furthermore, since the transparency, thermal stability, and light stability are better than that of polyvinyl chloride, these properties are actually improved.

As other compounding agents, anything that is used in polyvinyl chloride paste processing can be used. For example,
Reactive plasticizers, crosslinkers, fillers, heat stabilizers, light stabilizers,
Ultraviolet absorbers, epoxy compounds, dispersants, flame retardants, foaming agents, moisture absorbers, adhesives, pigments, thinners, antifoaming agents, mold release agents, and the like can be used according to conventional methods.

Next, I will explain how to make it into a sol, shape it, and mold it.
The method does not limit the content of the present invention, and any method may be used. The sol is prepared by uniformly kneading the various ingredients including the polyvinyl chloride paste resin, methacrylate resin, and plasticizer in a conventional mixer to obtain a uniform dispersion. As a mixer! Lanetary mixer, kneader 1 3 rolls, Hoha) Mi 4 sir
, i4 fry mixer, disilver, raikai machine,
Examples include a ribbon blender and a Henschel mixer. The mixed and homogenized sol is used with or without defoaming. Examples of defoaming methods include vacuum defoaming and vibration defoaming.

The prepared sol can be shaped into any desired shape using a processing machine. For example, Doctor Knife, Reverse O-Role, f f Erral Roll, 70 Fing Knife 7,
It can be coated onto the substrate using an air knife, curtain 70, etc. Further, it can be applied entirely or partially onto the substrate using a screen, an intaglio roll, a gravure roll, a spray, or the like. It can be formed into any desired shape by processing such as slot molding, shell molding, di- and f-molding, rotary molding, and casting. When heated, the shaped sol glues and melts, and when cooled, it becomes a tough molded product. The heating melting conditions are, for example, FJi 50C to 300Ct' about 0.5 to about 1
A condition such as 0 minutes can be exemplified.

(Effect of the invention) Thus, according to the present invention, compared to the prior art, the hardness,
It is possible to easily obtain polyvinyl chloride molded products with excellent matte, dry, and dry properties. When applied to the surface layer of flooring materials or wall materials, it becomes a product with a smooth finish with microscopic irregularities on the surface. When applied as a paint to coat the surface of metal, etc., a coating film with a hard, matte surface can be obtained. When applied to sheets and films, products with a dry-touch surface without stickiness can be obtained. Applications to tablecloths and leather provide products with a non-stick surface, while applications to gloves and immersion products prevent mold removal from adhesion and transfer of plasticizers to other materials with which they come into contact. It is easy to apply, and the texture of the product is also good. Having a non-adhesive surface of a molded product not only improves its performance as a product, but also improves its demoldability, ease of handling, and wrinkle resistance during the molding and distribution processes. It also has the advantage of preventing dust from adhering to it.

(Example) The present invention will be explained in more detail with reference to Examples below.

Note that parts and parts in Examples and Comparative Examples are based on weight unless otherwise specified.

The evaluation criteria are as follows.

Hardness: Hardness measured with a Duro A hardness meter.

Light reflectance at 60° reflection angle using a matte Nigelos meter.

Dry touch property: The degree of stickiness when touching the surface of a molded product with a finger is judged based on the following criteria.

◎ The surface is smooth and feels like paper ○ There is no stickiness and the feel is similar to paper △ There is a slight sticky feeling ＆: After leaving the sol after mixing and defoaming in an atmosphere of 23°C ± 2°C and relative humidity 50% ± 10% for 1 hour, Bm viscosity I
Viscosity measured using gt.

Moldability: The quality of the molded product (thickness, uniformity, strength) after shaping such as coating and heating and melting is judged based on the following criteria.

◎ Good ○ Good Δ Slightly problematic Defoaming was performed using a foam machine at 5 mxHg for 5 minutes.

Methacrylate resins with the composition, degree of polymerization, and particle size shown in Table 2 were synthesized and used. The sol composition was applied onto a glass plate to a thickness of 300 μm using a doctor blade 9, and then heated and molded at 200° C. in an open hot air circulation environment for 5 minutes. The table below shows the results of evaluating the molded sheet using the method described above.
Shown in 1.

Using the composition of the present invention, a molded article with good torability, matteness, and dry touch was obtained without impairing moldability.

Table 2 "MMA: Methyl methacrylate BA Nibutyl acrylate BMA Nibutyl methacrylate Example 6, Comparative Example 6 A sol having the composition shown in Table 3 was prepared in the same manner as in Examples 1 to 5, and a glove-shaped mold was used. A cold day test was conducted to examine hardness and dry touch properties.

The results are shown in Table-3.

Table-3

Claims (1)

[Claims] a. Resin for polyvinyl chloride paste, b. methacrylate resin and c. In the plastisol composition comprising a plasticizer, b is 90% by weight of methyl methacrylate.
A powdery polymer having an average molecular weight of 100,000 or more and an average particle size of 1 to 200μ, and having an a/b weight ratio of 20/80 to 95/
5. A plastisol composition characterized by: