JPS60262843A - Non-rigid polyvinyl chloride resin composition for composite with urethane resin having improved adhesiveness - Google Patents

Abstract

PURPOSE:To provide the titled compsn. excellent in adhesion to urethane resins, by incorporating magnesium oxide in polyvinyl chloride resins. CONSTITUTION:100pts.wt. polyvinyl chloride resin, about 30-400pts.wt. plastsizer (e.g., lowly volatile trimellitate plasticizers, which may be replaced by epoxy plasticizers within a range of about 0.3-20pts.wt.), 0.1-5pts.wt. finely powdered magnesium oxide and, if necessary, any other additives (e.g., stabilizers, antioxidants, colorants) are mixed homogeneously using stirring devices such as mixers, extruders, etc. Moldings comprising the resulting non-rigid polyvinyl chloride resin compsn. are excellent in adhesion to urethane resin moldings (e.g., urethane foam) and capable of forming composites not causing delamination, being well suited for manufacturing internal automotive trims, interior decorations, furniture mountings, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a soft vinyl chloride resin composition, and particularly to a composition containing a component that improves the adhesive strength of a composite between a molded article and a urethane resin.

"Prior Art" Conventionally, soft vinyl chloride resin has been widely used for interior materials of automobiles, such as crash pads, armrests, headrests, ceilings, doors, glove box lids, rear seats, etc.

In particular, soft vinyl chloride resin molded products are used in the form of a composite with a urethane resin that has a soft urethane foam inside to increase safety and flexibility.

However, in the case of soft vinyl chloride resin molded products that have low adhesion to urethane resin, partial peeling occurs between the soft vinyl chloride resin molded products and the urethane resin during use, resulting in wrinkles in the product and soft This has the disadvantage that the vinyl chloride resin molded product may become wavy, which may impair its practical value.

In order to prevent this drawback from being exposed, the current situation is that the automobile industry itself specifies the peel strength of each automobile part and has it delivered to the automobile parts manufacturer. That is, generally 0
．． ．． 3Ky/ko! A peel strength of 2 or more is required.

By the way, the peel strength of a composite of a hard vinyl chloride resin molded product and a urethane resin is
It usually exhibits a value of 0.3 Kp/koS■ or more, and since the molded product undergoes little deformation under pressure, there is no problem in terms of adhesion.

"Problems to be Solved by the Present Invention" The present inventors have conducted intensive studies to improve the adhesion between soft vinyl chloride resin molded products and urethane resin without using adhesives, and found that They discovered that by adding a small amount of magnesium oxide to a resin composition, the adhesive strength between a molded article obtained from the composition and a polyurethane resin was improved, and the present invention was completed. An object of the present invention is to provide a composition that improves the adhesive strength of a composite of a soft vinyl chloride resin molded product and a urethane resin.

"Structure of the Invention" The gist of the present invention is to provide an improved adhesive characterized in that magnesium oxide is contained in an amount ranging from 0.1 to 5 parts by weight per 100 parts by weight of a vinyl chloride resin. A soft vinyl chloride resin composition for a composite with a urethane resin having properties.

The present invention will be described in detail.

The vinyl chloride resin, which is one of the components constituting the soft vinyl chloride resin composition of the present invention, can be prepared by suspension polymerization, bulk polymerization, fine suspension polymerization, or a mixture of vinyl chloride or vinyl chloride and a comonomer copolymerizable therewith. Any material produced by a conventional method such as a polymerization method or an emulsion method can be used. Examples of comonomers that can be copolymerized with vinyl chloride include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate, acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, methyl methacrylate, and ethyl acrylate. Methacrylic acid esters such as methacrylate, maleic acid esters such as dibutyl maleate and diethyl maleate, phthalic acid esters such as dibutyl fumarate and diethyl fumarate, vinyl methyl ether, vinyl cyphthyl ether, vinyl octyl ether vinyl ethers such as acrylonitrile, vinyl cyanides such as methacrylate trile, α- such as ethylene, propylene, styrene, etc.
Examples include olefins, vinylidene chlorides other than vinyl chloride, such as vinylidene chloride, and vinyl bromide, and vinylidene rhodanides. It is used in a range of 20% by weight or less. Of course, the comonomers are not limited to those mentioned above.

As the softener, which is the other component constituting the soft vinyl chloride resin of the present invention, a plasticizer, plastic polyurethane, polylactone, etc. are used.

Plasticizers include, for example, di-n-butyl phthalate, di-n-octyl phthalate, dicoethylhexyl phthalate, 7
Diisooctyl talate, octyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, dicoethylhexyl inphthalate, or number of carbon atoms //~
7-thalic acid plasticizers such as phthalate esters of higher alcohols of about 73, trimellitic acid plasticizers such as n-osyl trimellitate, tri-octyl trimellitate,
Dicoethylhexyl adipic acid, di-adipate
n-decyl, diisodecyl adipate, dicoethylhexyl azelaate, senoxin Z Schiffl, seno (fatty acid ester plasticizers such as di-ethylhexyl sinate, tributyl phosphate, tri-U-ethylhexyl phosphate, Phosphate ester-based preparations such as 2-ethylhexyldiphenyl and tricresyl phosphate, epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil fatty acid-monoethylhexyl, etc., or epoxy-based plastics such as liquid epoxy resin. These electrodes or a mixture of two or more of them are used.

In order to provide a molded article with low fogging properties, a trimellitic acid plasticizer with low volatility or an ester plasticizer of higher alcohol and heptatalic acid is preferably used in the soft vinyl chloride resin composition.

The liquid epoxy resin mentioned above is slightly different from secondary plasticizers such as epoxidized soybean oil, but it contributes to thermal stability like epoxy plasticizers such as epoxidized soybean oil, and is liquid. In the present invention, it is included in the category of epoxy plasticizers. Liquid epoxy resins include, for example, bisphenol A type resins, cycloaliphatic resins, polybutadiene derived resins having 7 epoxy groups in the molecule, or resins with 7 epoxy groups per molecule.
Epoxy novolac resins having more than 1 epoxy groups are used.

The epoxy equivalent weight of these resins is usually higher than that of epoxidized soybean oil, typically 100-/! ;00° Preferably, a value of about /SO to 700 is used.

Therefore, the amount of plasticizer to be used is appropriately selected depending on the moldability, processability, workability of the composition, the use of the molded product, etc., but it is generally 30-0 parts by weight based on 100 parts by weight of the vinyl chloride resin.
00 parts by weight, preferably in the range of Sθ to 2QO parts by weight.

If the amount is less than 30 parts by weight, the peel strength will be 0.39/cojM or more even without the addition of magnesium oxide, which will only be economically disadvantageous. In addition, if the amount exceeds -00 parts by weight, the effect of improving adhesion is poor, and especially if it exceeds -00 parts by weight, it is unsuitable for use as an automobile interior material. Some of the aforementioned preferred plasticizers may be epoxidized soybean oil, epoxidized linseed oil, or epoxy resins, especially epoxidized linseed oil or epoxy resins.
By substituting in parts by weight, preferably in the range of /~SX-m parts, it greatly contributes to the heat resistance and light resistance of the vinyl chloride resin composition when made into a urethane resin composite without deteriorating the fogging performance. .

When the amount of the epoxy plasticizer added is less than parts by weight of O,S, it is difficult to obtain sufficiently satisfactory effects on heat resistance and light resistance.On the other hand, when the amount is more than parts by weight of O, the epoxy plasticizer may bleed. If the composition is a sol, the viscosity of the sol becomes high and processability is reduced.

In the case of a sol composition, part of the plasticizer can be replaced with a diluent such as texanol isobutyrate, dodecylbenzene, or kerosene, or an organic solvent that swells the vinyl chloride resin such as toluene or xylene. It may also be used in the form of The gradual addition amount of diluent and organic solvent is
It is determined as appropriate depending on the usage.

The plastic polyurethane used to soften the vinyl chloride resin is a linear one, and the polylactone used is a polylactone prepared by open polymerization of various lactones.

These polyurethane and polylactone are used in appropriate amounts depending on the degree of softening of the vinyl chloride resin composition. Molded products obtained from vinyl chloride resin compositions softened with polyurethane or polylactone are less economical, but have good migration properties, excellent fogging performance, and good adhesion to urethane resins. give.

In the present invention, the magnesium oxide contained in the soft vinyl chloride resin is not particularly limited, but is preferably in the form of fine particles in order to be uniformly dispersed in the composition. Preferably, the amount is in the range of 0.1 to 3 parts by weight, particularly 3 parts by weight or less, per 10[theta] parts by weight. When the amount added is less than 0.1 part by weight, the effect of improving adhesion can be sufficiently exhibited, whereas when it is more than 0.1 part by weight, it is
This is undesirable because it tends to cause discoloration, which is generally referred to as "burning".

The soft vinyl chloride resin composition of the present invention contains various additives normally used in vinyl chloride resins, such as stabilizers, antioxidants, ultraviolet Mg and absorbers, fillers, colorants, release agents, etc. O Soft vinyl chloride resin compositions and molded articles, in which O is often used in combination, are prepared or molded as follows.

The soft vinyl chloride resin composition is prepared by adding the above-mentioned essential ingredients and other additives depending on the quality of the ingredients to a high-speed mixer, kneader, ribbon pretender, roll, Banbury mixer 1 extruder, or other mixer or mixer. It is adjusted by uniformly blending using.

For example, in order to produce a soft vinyl chloride resin composition from a vinyl chloride polymer obtained by suspension polymerization or bulk polymerization, it is necessary to add cyclized vinyl resin, essential components such as plasticizers and magnesium oxide, stabilizers, etc. By adding other additives,
Mix uniformly with a ribbon blender, high-speed stirrer, dry rough, and if necessary use a roll or Banbury mixer.
1. After heating and melting in a kneading machine such as an extruder, it may be formed into a sheet or strand, and this may be shaped into a pellet using a sheet cutter or petizer. The resin composition is generally made into a molded article by injection molding or blow molding.

In addition, in order to produce a soft vinyl chloride resin composition for powder molding, the particle size Sθ~/! After homogeneously mixing vinyl chloride resin of about 0.01tm with magnesium oxide and plasticizer and hot tri-blending, it is cooled to SO ~ 70℃, and at that temperature it is inorganic with a particle size in the range of 0.00 / ~ 10μ. A manufacturing method is adopted in which a fluidity improver made of a compound powder, a powdered thermoplastic resin, etc. is added and uniformly coated on the surface of a hot tri-blended vinyl chloride resin. Examples of fluidity improvers include vinyl chloride resins produced by emulsion polymerization or fine suspension polymerization, polymethyl methacrylate, styrene-7-crylonitrile copolymers, and finely divided silicon oxide. It is selected appropriately depending on the body molding method, moldability, workability, workability, etc., but generally 30 parts by weight per 100 parts by weight of the vinyl chloride polymer.
It is not more than 3 parts by weight, preferably in the range of S to 3 parts by weight.

Of course, the composition for powder molding is simply a vinyl chloride resin,
A hot tri-blend of magnesium oxide, a stabilizer, a plasticizer, etc. can also be used, and the addition of a fluidity improver is not necessarily required. The composition thus produced is used in the Engel process, Heisler process, Hayashi process, fluidized dip coating, electrostatic powder coating, rotational molding, and the like.

When the soft vinyl chloride resin composition is a sol composition such as plastisol or organosol, magnesium oxide, stabilizers, plasticizers, etc. are simply added to the vinyl chloride resin produced by emulsion polymerization or fine suspension polymerization. It is manufactured by uniformly mixing with a mixing agitator such as a mixer or a kneader. The sol composition is used for rotational molding, slush molding, etc., and specifically, it is molded as follows. A predetermined amount of the sol composition is poured into a mold for molding the intended surface material, and the melting temperature is set to
The molded product is heated for about 5 to 12 Q minutes to melt, then cooled and the molded product is removed from the mold.

The molded article made of the soft vinyl chloride resin composition molded as described above is used as a composite with a urethane resin. To compound urethane resin into a molded product, for example, polyisocyanate, polyol, blowing agent, catalyst, cell size regulator, etc. are mixed in a short time using a mixer, and the mixture is jetted into the molded product to form polyurethane foam. Well-known methods are employed.

"Effects of the Invention" According to the present invention, even if the vinyl chloride resin molded product is manufactured from a soft composition, since the composition contains magnesium oxide, the composition does not contain magnesium oxide. It has better adhesion to urethane resin and improved releasability compared to molded products made from urethane resin. and,
Since the molded product and the urethane resin do not easily separate, wrinkles and wavy phenomena do not occur in the vinyl chloride resin molded product.

Therefore, the present invention provides interior materials, ceiling materials, wall materials, floor materials such as vehicle ceiling materials, wall materials, glove box lids, rear parcels, armrests, headrests, crash pads, etc., which are composites of vinyl chloride resin molded products and urethane resins. It has extremely high utility value in the production of interior materials for houses such as houses, as well as furniture covering materials.

"Example" Next, the present invention will be explained in detail with reference to an example, but the present invention is not limited to the following example unless it exceeds the gist thereof.

In addition, in the examples, the term "part" indicates "sumire part".

Examples / - Comparative Examples / Vinyl chloride resin 100 parts (suspension polymerized product, particle size about 15 μm, average degree of polymerization 200) Phthalate ester plasticizer 75 parts (number of carbon atoms? - / / mixture value Ester of alcohol) Epoxidized soybean oil 5 parts Ba-Zr) Stabilizer 3 parts Magnesium oxide Predetermined parts The above blended composition was hot tri-blended in a super mixer, cooled to about SO℃, and emulsified as a fluidity improver. A B14 soft vinyl chloride resin composition for powder molding was prepared by uniformly coating the surface of a hot tri-blend product with a base resin θ part manufactured by a legal method. The composition was melted on a heated flat metal plate to produce a sheet having a wall thickness of about 7 mm (hereinafter referred to as 1 powder 1 molded product). The JIS A hardness of the sheet was 7g.

Separately, a soft vinyl chloride resin composition for powder molding was kneaded with a roll to produce a sheet having a wall thickness of approximately 7 mm (hereinafter referred to as "kneaded molded product").

Each of the obtained sheets was placed in a mold for polyurethane foam, and after foaming and laminating about lθ urethane resin on top of the sheet, it was poured out from the mold to form a composite test piece for a peel test. I cut it out.

These test pieces were subjected to a peel test between the vinyl chloride resin molded product and the urethane resin, and the results are shown in Table 7.

In the case of the powder molded product of Comparative Example/ in which no magnesium oxide is added in Table 7, O, JK9/, 2 as specified by the automobile manufacturer.
It can be seen that the value of jsm is not reached.

In addition, as the amount of magnesium oxide added increases, the peel strength increases, which shifts to a favorable direction in terms of adhesion, and the addition of magnesium oxide widens the allowable range for adhesion of polyvinyl chloride resin molded products to urethane resin. I understand.

In the case of kneaded molded products, even if magnesium oxide is not added completely, it shows a value of 9/Jjm at 0.44, which is 0.3~/,2! ; wsx has been achieved, but the peel strength usually decreases due to the mixing of lubricants, mold release agents, etc. into the soft composition, so the peel strength is improved by adding magnesium oxide and the punch capacity range of adhesiveness is increased. It is desirable to keep it elevated.

Example S, 100 parts of vinyl chloride W fat used in comparative comparison Example/, Example/
Part of the plasticizer used in tS, part of epoxidized linseed oil, Ba
- Prepare a soft vinyl chloride resin composition containing 2 parts of Zn-based stabilizer, 0 parts or 0.3 parts of calcium carbonate SS, and 0 parts or 0.3 parts of magnesium oxide. A sheet was molded and the difference in peel strength between the urethane foam and the urethane foam was compared between the presence and absence of magnesium oxide. The JISA (i!) of the sheet was 4Q. The composite method with the urethane resin was the same as in Example.

As a result, when magnesium oxide was not added, the peel strength did not reach the value of 0.3 K4/2 j m, and when magnesium oxide was added, the peel strength was greater than 0.3 K4/2 S wsa.

As described above, depending on the compounding composition, even when a kneaded molded product is made, the value of 0-3 Kylsr tone may not be achieved in some cases, so it can be seen that the addition of magnesium oxide is extremely effective in terms of adhesion to urethane resin.

Patent Applicant Mitsubishi Monsanto Chemical Vinyl Co., Ltd. Agent Patent Attorney Hase - #1 or Name

Claims (4)

[Claims] (1) 0.1 to 5 per 100 parts by weight of vinyl chloride resin
A soft vinyl chloride resin composition for a composite with a urethane resin having improved adhesion, characterized by containing magnesium oxide in an amount in the range of parts by weight. (2) The composition according to claim 1, wherein the soft vinyl chloride resin composition is glastisol or organosol. (3) The composition according to claim 1, wherein the soft vinyl chloride resin composition is a resin composition for powder molding. (4) Composition 0 according to claim 1, wherein the urethane resin is a urethane foam.