JPS58217540A - Polyvinyl chloride plastisol composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. capable of giving an arbitrary gloss level without requiring any physical after-treatment stages, by blending polyvinyl chloride paste resin, polyvinyl chloride blending resin and a plasticizer in a specified ratio. CONSTITUTION:40-90pts.wt. resin (A) consisting of 1-100wt% polyvinyl chloride paste resin (particle size of 10mu or below, average degree of polymn. of 2,000 or above, tetrahydrofuran-insoluble gel component of 4wt% or below) and 99-0wt% polyvinyl chloride paste resin (particle size of 10mu or below, average degree of polymn. of 2,000 or above, gel component of 0wt%), 60- 10pts.wt. polyvinyl chloride blending resin (B) having an average particle size of 10-100mu and 30-100pts.wt. (per 100pts.wt. of the combined amount of components A and B) plasticizer (C) such as di-n-butyl phthalate, are blended together.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyvinyl chloride plastisol compositions that are capable of obtaining any desired gloss level from a glossy state to a so-called matte state without physical post-treatment steps.

In recent years, the field of flooring materials has come to require a high level of quality due to the switch to glass paper base materials and the development of functional flooring materials for heavy walking applications.

Recent performance requirements for the top layer of flooring materials include (i) Eliminating gloss without significantly reducing transparency; ■ Excellent mechanical properties and moderate flexibility; and ■ Chemical embossability. Things that don't make things worse ■ Easy secondary processing and no heat deformation during reheating.In particular, in response to requests to remove luster,
For example, ■ A base resin with an average polymerization density of about θO to 20θ0 has a large particle size of 10θ produced by a suspension polymerization method.
A method of producing a sheet with a matte surface by heating a vinyl chloride resin of about μ or a plastisol with an average degree of polymerization of about Qθθ and ~jθ% above the melting temperature of paste resin. A method of applying a matting surface treatment agent to the obtained sheet by heating it above a specified temperature and cooling it, and reheating it if necessary. A method of producing a sheet with a matte surface by embossing it using plastisol, ■ Adding a silicon-based filler etc. to plastisol as appropriate, heating it above the melting temperature and cooling it to obtain a sheet with a matte surface. There are various methods, but method (①) is only effective within an extremely narrow temperature range with limited heating conditions and is industrially inconvenient, and method (③) requires a surface treatment agent and the process of applying it. The method @ requires embossing equipment, and the method ■ increases the viscosity of the plastisol due to the addition of fillers, making processing inconvenient and difficult, and the resulting sheet has poor transparency. Each of these methods had various drawbacks, and none of them were satisfactory.

Also, glossy? Although not intended for portraiture, a plastisol composition consisting of a base resin containing 5 to 10% by weight of gel content was disclosed in Japanese Patent Application Laid-Open No. 7-7-2011. Although it is disclosed in Japanese Patent Application No. 9232, the permeation rate of the plasticizer is slow due to the relatively high degree of crosslinking within the Paston 2F particles.
Under normal heating conditions, gelation and melting do not proceed completely, resulting in a product with poor transparency, tensile properties, and tear properties, and the high melt viscosity results in extremely poor chemical embossability. There was a drawback that it resulted in an inferior product 1τ.

The present inventors conducted extensive research on a method for easily obtaining a matte surface without deteriorating the properties necessary for the top layer of the legal phase, such as water resistance, weather resistance, thermal stability, and processability. By using a paste resin with an extremely low degree of polymerization or a high average degree of polymerization without crosslinking, heating can be performed in an extremely wide temperature range without using a matting agent or without going through a matting process. It has been found that the desired matte surface can be obtained under the conditions,
The present invention has now been completed.

That is, the object of the present invention is to produce a matte surface of any gloss level from a transparent glossy state to a so-called transparent matte state without using a matting agent or undergoing a matting treatment process. An object of the present invention is to provide a polyvinyl chloride plastisol composition from which a molded article having the following properties can be obtained.

Therefore, the gist of the present invention is (a) average degree of polymerization θθθ
% by weight of a gel that is insoluble in tetrahydrofuran or more
A polyvinyl chloride base resin consisting of the following vinyl chloride base resin / ~ 100% by weight and a polyvinyl chloride base resin tough ~ θ weight % of average polymerization concentration -θOθ or less and without gel content is used in a weight ratio of 0 to 100% by weight. 0 parts, (b) 70 to 60 parts by weight of vinyl chloride pregin resin with an average particle diameter / θ ~ 100 μ, and (C) 30 parts by weight of plasticizer per 700 parts by weight of the resins in (a) and (b) above. ~/θ0
The polyvinyl chloride plastisol composition consists of parts by weight.

To explain the present invention in detail, the vinyl chloride paste resin (hereinafter referred to as base resin) used in the composition of the present invention has a homopolymerization degree of -000 or more and a tetrahydrofuran (hereinafter referred to as THF) K-insoluble gel content of 4% by weight or less. (referred to as A)
is a copolymer obtained from a vinyl chloride homopolymer or a mixture of vinyl chloride and a comonomer copolymerizable therewith, produced by an emulsion polymerization method or a fine suspension polymerization method, and is produced at a relatively low temperature, e.g. Those polymerized in the reaction temperature range of °C, or diallyl esters of phthalic acid such as diallyl phthalate, diallyl esters of ethylenically unsaturated dibasic acids such as diallyl maleate, and diallyl esters of saturated dibasic acids such as diallyl phthalate. , triallyl cyanurate, triallyl isocyanurate, divinyl ethers such as ethylene glycol divinyl ether, dimethacrylic esters or diacrylic esters of polyhydric alcohols such as ethylene fl/j-dimethacrylate, trimethylolpropane trimethacrylate, etc. It is made by adding a small amount of trimethacrylic ester or triacrylic ester of a polyhydric alcohol and polymerizing it at a relatively high temperature, resulting in slight crosslinking. With these polymerization methods, the average degree of polymerization is preferably 200θ or more, λ! θO~soo.

In particular, those with a diameter of 2 ta 0 θ to gu θ θ θ are manufactured.

Base Resin A is preferably non-crosslinked, and for the purpose of matting, it is desirable to appropriately select the blending ratio and average degree of polymerization of Base Resin A to maintain transparency and mechanical properties. . Of course, it may be slightly cross-linked, but the degree of cross-linking is determined by dissolving in KO'CTHF for 2 hours and then centrifuging (/θ, θθOaX≦θ minutes).The ratio of the remaining weight to the initial M amount is up to % by weight. It is necessary to keep it at that. Although the degree of polymerization may be higher than SOθθ, for example, if the degree of polymerization is about OOOθ, the gel content may be close to J% by weight according to the above measurement method, and the resulting product will have poor transparency and physical properties. It becomes like this.

Vinyl chloride base resin with an average degree of polymerization of 2000 or less and no gel content (hereinafter referred to as paste resin B) is
Commercially available vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith produced by a conventional emulsion polymerization method or a fine suspension polymerization method can be used.

Base Resin A People's Paste Resino BK Sealing comonomers include, for example, ethylene, propylene, butene, pentene/butadiene, styrene, α-methylstyrene, vinegar] Vinyl esters such as caproic acid, caprylic acid, benzoic acid, etc. or allyl esters, dialkylmaleic acid or fullalic acid esters with carbon atoms in the alkyl group /~/J (cl~12), acrylonitrile, vinylidene chloride, didene cyanide, alkyl groups with 01-12 Examples include alkyl vinyl ethers, N-vinylpyrrolidone, vinylpyridine, vinylsilanes, acrylic acid alkyl esters of alkyl groups 01 to 16, or methacrylic acid alkyl esters, and at least one of these is combined with vinyl chloride 7
It can be copolymerized in an amount of 70 parts by weight or less, preferably 3θ parts by weight or less, based on 00 parts by weight.

Mata, Base Resin A J □: Base Resin B
The particle size of is usually in the range of 70μ or less θ, / ~ jμ, and the blending ratio of the two is such that the former is in the range of 7 to 700% by weight and the latter is in the range of 72 to 0% by weight, especially the former is in the range of 30% by weight. It is preferable to use a vinyl chloride base resin containing at least % by weight.

Vinyl chloride blend resin, which is an essential component of the present invention, needs to have an average particle diameter of 70 to /θ0μ, and has the effect of lowering the viscosity of plastisol.

The blending blend usually consists of vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith.
Manufactured by turbidity polymerization method.

Therefore, the mixing ratio of the vinyl chloride base resin and the salted vinyl blending resin is expressed in parts by weight, and is 0 to 9θ, ≦θ to 10, preferably jO to fj:jθ-
It is preferable to select from the range of /j so that the total amount is 700 parts by weight.

Furthermore, in the mixture of vinyl chloride base resin and vinyl chloride pregin resin, base resin A is Oi based on the total amount, that is, based on the total vinyl chloride resin.
It is desirable that the content is at least 10% by weight, preferably at least 10% by weight, particularly at least 1jM%.

The plasticizer used in the composition of the present invention is not particularly limited as long as it is used in ordinary vinyl chloride resins, but examples include di-n-butyl phthalate, di-n-octyl phthalate, Phthalic acid plasticizers such as dicoethylhexyl phthalate (DOP), diisooctyl phthalate, octyldene phthalate, diindecyl phthalate, phthylbenzyl phthalate, di-ethylhexyl inphthalate, di-ethylhexyl adipinoate (D
OA), fatty acid ester plasticizers such as di-n-decyl adipate, diisodecyl adipate, di-ethylhexyl azelate, dibutyl sebacate, dicoethylhexyl sebacate, tributyl phosphate, tri-2-ethylhexyl phosphate, phosphoric acid Phosphate ester plasticizers such as -2-ethylhexyldiphenyl and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil and epoxidized tall oil fatty acid -2-ethylhexyl; Use a mixture of more than one species. The amount of plasticizer to be used is appropriately selected depending on the desired solid content concentration, fluidity, product application, etc. of plastisol, and is 30 to θO weight based on the total N700 parts by weight of vinyl chloride base resin and vinyl chloride pregin resin. Department,
Preferably it is in the range of 90 to 70 parts by weight.

In addition, some of the plasticizers are diluents such as texanol isobutyrate and dodecylbenzene, alkaline or toluene,
It can be replaced with an organic solvent that swells the vinyl chloride resin, such as xylene, or an organosol. The amount of the diluent and organic solvent to be added is appropriately determined depending on the application within a range of 75 parts by weight or less.

The polyvinyl chloride plastisol composition of the present invention is prepared by mixing the above-mentioned essential components or additives that are usually added to vinyl chloride resin, such as stabilizers, antioxidants, and ultraviolet absorbers, using a high-speed mixer, kneader, etc. Manufactured by uniformly mixing with a stirrer. Then, the composition is coated on a base material or poured in a predetermined amount into a mold, etc., to a gelling temperature of, for example, /2 to 2.
It is heated at J-θ°C for about 0.5 to 20 minutes to gel.

The sol composition of the present invention can be made transparent under heating conditions with a wide range of temperature and expansion range by simply changing the polymerization degree and amount of the base resin to be blended, without using a matting agent or performing matting treatment. Moreover, it is possible to produce a molded article having a desired matte surface, and the molded article has the same water resistance, weather resistance, thermal stability, and processability as conventional products. Therefore, the sol composition of the present invention is suitable for use in the top layer of flooring materials and the surface layer of walls, and has extremely high industrial utility value.

The present invention will be explained in detail below using Examples, or the present invention is limited to the following Examples unless the gist of the invention is exceeded.

l Gloss: Crossmeter manufactured by Nippon Heavy Industries (Va-10)
), the sheet obtained from the plastisol composition was irradiated with light at an incident angle of 6θ0 to the perpendicular line, and the reflected light at an angle of 600 was measured. The smaller the number, the less glossy.

2 Transmittance: Hitachi spectrophotometer type 3-3, wavelength spear! θm
The amount of transmitted light of μ was measured.

3. Visibility of the base (pattern) 2. Visually check 0, △, or dull Monovalent [−] in three stages of ×.

4 Tensile properties: J engineering 5K-673, 2 remaining, elongation is J
ISj dumbbells and right angle dumbbells are used for tearing.

5. Chemical embossability: A flooring material was manufactured as described below, and the angle α and valley length l in the attached cross-sectional view of the flooring material were measured using a small plate universal surface profile measuring device (SE-3h). The drawing is a cross-sectional view of the flooring material. In the drawing, / indicates the foam layer and C indicates the top layer, respectively.

Examples/~3, Comparative Examples/~- (A) Top layer blended plastisol base resin 600 parts by weight Prenzin resin polymerization degree pioθ glue O dioctyl phthalate (
D Q P) Kθ dodecylbenzene (DDE
), J-epoxidized soybean oil
-f3a-Zn stabilizer
°3 Place the top layer compounded plastisol on the glass plate o, x
Coated with sma thickness, 200℃, 2/! °C, 2
The sheet was gelled by heating for 3 minutes in an open environment at 30° C., and after cooling, the gloss, permeability, and tensile properties (2/, heated at f° C. were used) of the obtained sheet were measured.

(B) Plastisol base resin containing foam layer (p/θ0θ) 200 parts by weight Blazin Blazin P/θθO)3θD OP
, l0
DDE
Taazodicarbonamide (foaming agent)
21.2 Zn stabilizer 0.6 Calcium carbonate λθ titanium oxide
j Plastisol containing a foam layer was added to glass vapor soil with a thickness of 0.3 tmm! After coating with a thickness of 17 nm and gelling, a pattern transfer paper partially coated with a chemical embossing agent was transferred at 720°C for a minute, and then a top layer of plastisol was applied on top of the pattern transfer paper with a thickness of 17 nm. It was coated to a thickness of 26 mm and heated at 0° C. for 7 minutes and 50 seconds. The chemical embossability and workability of the flooring materials after cooling were evaluated.

Next, the back side of the glass paper was coated with Glastisol containing the same foam layer to a thickness of 35 mm, and then heated at 7θ°C for 1 minute, and the thermal deformability of the layer was determined.

These results are shown in Table/.

Comparative Example/, which has a low average degree of polymerization, has poor gloss and heat deformability, while Comparative Example -, which has a high p content, has poor transparency and physical properties due to the large gel content, and is not satisfactory in chemical embossability.

A satisfactory transparent matte surface can be obtained under heating conditions over a wide temperature range in the examples in which p is 2000 or more and gel fraction is % or less.

Example Group B, Comparative Example 3 The same procedure as in Example 1-3 was carried out except that the proportions of the base resin and blending resin in the top layer of glastizol in Example 1-3 were changed.

For comparison, the same procedure was carried out for a base resin with a gel content of j and %, and the results are shown in the table.

It can be seen that by changing the blending ratio of the base resin and the blending resin and by changing the gelling temperature, it is possible to produce a sort with a wide range of matte surfaces without impairing properties such as chemical embossability. In addition, in the case of gelation at 23θ°C, it tends to become a little glossy, so it is preferable to use blending resin in an amount equal to or greater than Yushige mansion.Example 7, plasticizer Table 3 shows the results of examining the matte state by varying the amount used.

Table 3: When the amount of plasticizer is increased, problems arise in heat deformability. However, it is judged that there is no problem depending on the usage.

From the above results, when the base ton shift p is less than 2θθθ, gloss tends to appear, and conversely, even if p is 2000 or more, when the gel content is 3% or more, the matteness is good, but the transparency is low. It is clear that the tensile properties and chemical embossing properties also become extremely low.

[Brief explanation of the drawing]

The drawing is a cross-sectional view of the law phase. In the figure, / represents the foam layer, and 0 represents the top layer coated with the composition of the present invention, respectively. Patent applicant Mitsubishi Monzant Chemical Co., Ltd. Representative
Person Patent Attorney Hase Yo − Others/Names

Claims (1)

[Claims] (1) (a) Vinyl chloride base resin with an average degree of polymerization of 2000 or more and less than % by weight of gel fraction insoluble in tetrahydrofuran/~/θO'NLX% and average degree of polymerization -2
90 to 20 parts by weight of a polyvinyl chloride base resin consisting of Tough ~ 0% by weight of a vinyl chloride base resin with a particle size of 00θ or less and no gel content (b) A vinyl chloride base resin with an average particle size of 10 to ioo μ by weight A polyvinyl chloride plastisol composition comprising 0 to 70 parts by weight of a plasticizer and (C) 30 to 100 parts by weight of a plasticizer per 700 parts by weight of the resins (a) and (b).