JP2001270971A - Plastisol composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic plastisol composition having a good flowability as the sol and, in addition, excellent shelf life, good molding porocessability, and to provide a molded article with good appearance, safely handled and excellent heat resistance and capable of easily attaing a high level of quality control of products. SOLUTION: In the acrylic resin plastisol composition consisting of an acrylic resin powder and a plasticizer as the major components. A condensed phosphoric acid ester is used as the plasticizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sol having good fluidity, excellent storage stability, good moldability,
The present invention relates to an acrylic resin-based plastisol composition having good appearance, safety, heat resistance, and the like of a molded product and easily controlling the hardness of the product. An example of a more specific application field is a strippable primary mask (a strippable mask) used to partially form a film so that solder does not adhere in a process such as soldering, and to peel it off after soldering. And a spacer material for a keyboard (membrane keyboard) using a flexible substrate.

[0002]

2. Description of the Related Art A plastisol is a fluid high-viscosity paste in which a resin powder is dispersed in a plasticizer, and is applied to an article by means such as spray coating, dip coating, screen printing, and then heat-treated. A resin powder swells with a plasticizer and gels to change into a flexible film, and is widely used in fields such as resin films, toys, gloves, and undercoating of automobiles. A typical plastisol is a vinyl chloride resin (hereinafter referred to as PVC).
Abbreviated. ) Is well known in combination with a phthalate plasticizer. However, since PVC contains chlorine as a component, pollution due to hydrogen chloride gas and dioxin generated during combustion is suspected, and dioctyl phthalate (DOP), a typical phthalate plasticizer, is suspected of being an environmental hormone. Yes, recently
Conversion of VC and de-DOP to plastisol is urgent.

[0003] Against this background, an acrylic resin-based plastisol in which an acrylic resin-based powder is combined with a plasticizer has been proposed. Japanese Patent Publication No. 55-16177 proposes a plastisol in which a specific acrylic resin is mixed with a plasticizer. Among these, the important issues that plastisols should have are compatibility of resins and plasticizers and storage stability of sols. Concerning the compatibility between the resin and the plasticizer, for example, PMMA (polymethyl methacrylate) and phthalate plasticizer DBP (dibutyl phthalate) have poor compatibility, and the plasticizer oozes out from the gelled film. About 5 in MMA (methyl methacrylate)
It is stated that acrylic resins copolymerized with -25% butyl methacrylate have improved compatibility with DBP. The storage stability is such that the viscosity after leaving the sol at room temperature for 8 days is 3 times or less of the initial value, and that there is an optimum particle size and glass transition temperature of the specific acrylic resin depending on the type of the plasticizer. . Also, Japanese Unexamined Patent Publication No. 7-25953
No. proposes a core-shell polymer in order to obtain a plastisol having good workability (flowability) at room temperature, excellent storage stability and no bleeding of a plasticizer from a thermoformed film. Also, in JP-A-8-165398,
A specific acrylic resin copolymer in which a plasticizer and an acrylic monomer are combined, JP-A-8-295850 discloses an acrylic resin copolymer having a grangent structure in which a plasticizer and a filler are combined, and Further, an organic solvent has been proposed.

Japanese Patent Application Laid-Open No. 10-298391 discloses that
It is stated that in a plastisol composed of PMMA and a plasticizer (benzoic acid ester), storage stability is improved by using a resin having two or more peaks in a particle size distribution curve of an acrylic resin. However, in any of the prior applications, a plastisol having high storage stability that can be stored at 40 ° C. for about one month has not been developed. here,
The goal of being stable at 40 ° C for 1 month was determined based on an empirical rule that 40 ° C for 1 month is equivalent to 25 ° C for 3 months. Conversely, developing a plastisol that is stable at room temperature for about 3 months was required. Become a goal. By improving the storage stability of plastisol, a gelled product can be obtained under stable working conditions, and there is a great merit that the quality of the product is stabilized. Also, once gelled, it cannot be used as a plastisol and is discarded. Plastisols with good storage stability have the advantage of being economical and of effective use of resources because they can reduce this waste.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a sol having good fluidity, excellent storage stability, good moldability, good appearance, safety, heat resistance, etc. of the molded product and good product hardness. An object of the present invention is to provide an acrylic resin-based plastisol composition that can be easily controlled.

[0006]

Means for Solving the Problems In order to solve such problems, the present invention has been studied as a result of an intensive study on an acrylic resin-based plastisol composition containing an acrylic resin-based powder and a plasticizer as main components. By using a condensed phosphoric acid ester and, if necessary, further adding a hydroxy fatty acid ester, it was found that all of the above problems were solved, and the present invention was completed. In the present invention, as the acrylic resin-based powder, a homopolymer (PMA) containing methyl methacrylate (MMA) as a main component is used.
MA) or a copolymer powder is used. These particles have a particle size of 0.5 to 100 μm, a molecular weight of 100,000 or more, and a glass transition temperature (Tg) of 50 ° C. or more, preferably 70 ° C. or more. Here, if the particle size is smaller than this value, the solubility in the plasticizer is increased even at a low temperature, and the stability as a plastisol is impaired. If the particle size is increased to a level of several hundred μm, fusion between particles becomes incomplete. In particular, under low heat treatment conditions, the tendency of gelation hardly increases, which is not preferable.

Further, when the Tg is 50 ° C. or lower, there is a problem that the gelled film remains sticky or the gel film strength is weakened. On the other hand, if the molecular weight is 200,000 or less, the gel film strength is low and the stability of the sol is poor, so that it is not preferable. As the acrylic resin-based powder used in the present invention, those commercially available from Zeon Corporation under the trade name of Zeon acrylic resin F series are used. For example, Zeon acrylic resin F301 (epoxy-containing MMA resin, particle size of about 2 μm,
Tg of about 100 ° C., molecular weight is unknown because of having a partially crosslinked structure), F303 (modified PMMA, particle size of about 2 μm), F3
20 (PMMA, particle size about 1 μm, Tg about 107 ° C., molecular weight 3 million), F325 (PMMA, particle size about 1 μm, T
g about 107 ° C, molecular weight 400,000), F340 (MMA copolymer, particle size about 1 μm, Tg about 90 ° C, molecular weight 3,000,000)
And so on. These acrylic resin powders can be used alone or as a mixture, but it is preferable to use a high molecular weight PMMA (for example, F320) as a base from the viewpoint of gel film strength and sol storage stability.

In the present invention, as a plasticizer, a condensed phosphate ester is used as a main component in consideration of film formability, volatility (thermal stability), and storage stability. TPP (triphenyl phosphate), TCP (tricresyl phosphate), TX which are known as conventional phosphate ester plasticizers
P (trixylenyl phosphate), CDP (cresyl diphenyl phosphate) and the like have a structure represented by the following formula (1), and are so-called monomers,
The condensed phosphoric ester has a structure that can be called a dimer as shown by the following formula (2).

(RO) ₃ P = O (1) (RO) ₂ P (O) -OR′-O- (O) P (OR) ₂ (2) where R is a phenyl group or a cresyl group , A xylenyl group and the like. R _{'is, -Ph- -Ph-C (CH 3} ) 2 -Ph- -Ph-CH 2 -Ph- Incidentally, Ph represents a phenyl group

That is, the structure has a structure in which two diphenyl phosphates or dicresyl phosphates are bonded to phenols having two hydroxyl groups in a molecule, such as resorcinol, bisphenol A and bisphenol F. Commercially available resorcinol bis (diphenyl phosphate) (RDP), bisphenol A bis (diphenyl phosphate) (BDP), bisphenol A bis (dicresyl phosphate) (BDC
P) and the like, which have recently attracted attention as flame retardants for engineering plastics.

The condensed phosphate esters having a dimer structure (2) used in the present invention, such as RDP and BDP, are:
Since the heat resistance is extremely superior to TCP and CDP having a monomer structure, the plasticizer hardly volatilizes in the step of heating and gelling the plastisol to form a film, and there is no odor in the working environment. There are features. Also, the heat resistance of the formed film is very good. For example, even if the film is heated at about 250 ° C. for about 10 minutes, there is no change in the film properties (when a conventional monomer type plasticizer is used, More than half of the film diffuses, making the film hard and brittle.) This can be easily understood from the results of the thermogravimetric analysis (FIG. 1).

In the present invention, these condensed phosphoric acid esters are used as a main component as a plasticizer, and it is also possible to mix another plasticizer having an affinity with the acrylic resin powder. Examples thereof include phosphate ester plasticizers such as TCP (tricresyl phosphate) and CDP (cresyl diphenyl phosphate), and benzoate ester plasticizers such as diethylene glycol dibenzoate and dipropylene glycol dibenzoate. Examples include polyethylene glycol dibenzoate and polypropylene glycol dibenzoate. In this case, the amount is preferably 0 to 50 parts by weight with respect to 100 parts by weight of the condensed phosphoric acid ester, depending on what kind of structure and physical property plasticizer is used in combination. If the amount is more than this, the heat resistance and storage stability of the plastisol composition generally deteriorate, which is not preferable.

In the present invention, the mixing ratio of the acrylic resin-based powder and the plasticizer containing a condensed phosphate ester as a main component differs in the required fluidity level such as the application of the plastisol and the film forming method. The viscosity and the type of additives (inorganic fillers and organic fillers, other resin components, adhesion promoters, surfactants, etc.) and the amount of the additives vary, but generally 100 parts by weight of acrylic resin powder The plasticizer of the present invention is used in an amount of 100 to 300 parts by weight, preferably 120 to 250 parts by weight. If the amount of the plasticizer is less than this range, the viscosity of the plastisol is too high and the fluidity is poor, and it is difficult to form a film. If the plasticizer is added beyond this range, the film strength generally decreases and the film is formed. Tack may remain on the applied film, which is not preferable.

In the present invention, by adding a hydroxy fatty acid ester to the above-mentioned plastisol composition of the present invention, it is possible to control the film properties (particularly, elastic modulus and elongation). Hydroxy fatty acid esters are castor oil fatty acids and 12-hydroxystearic acid,
It is obtained by esterifying one or both of an acid group and a hydroxyl group, has a low pour point, and has good compatibility with the acrylic resin-based plastisol of the present invention. Therefore, by controlling these types and amounts of addition, it is possible to adjust the film properties of the plastisol of the present invention in a wide range. Examples of the hydroxy fatty acid ester that can be used in the present invention include:
A pour point of −0 ° C. or lower methyl ricinolate, ethyl ricinolate, butyl ricinolate, ethylene glycol monomethyl ricinolate, propylene glycol monoricinolate, trimethylolpropane monoricinolate,
Sorbitan monoricinoleate, glyceryl triacetyl ricinolate, methyl acetyl ricinolate, butyl acetyl ricinolate, butyl 12-acetoxystearate and the like.

In the present invention, the mixing ratio of the plastisol composition of the present invention to the hydroxy fatty acid ester varies depending on the composition of the plastisol and the type of the hydroxy fatty acid ester used.
0 to 25 parts by weight is used per part by weight. If the amount of the hydroxy fatty acid ester is increased, the film becomes soft and easily stretched. However, if the amount exceeds this range, gelation becomes difficult or the heat resistance is lowered in many cases, which is not preferable.

The acrylic resin-based plastisol composition of the present invention comprises a specific acrylic resin-based powder and a specific plasticizer as main components.
Inorganic filler such as talc, barium sulfate, silica, alumina or silicone resin, phenol resin,
Melamine resin, benzoguanamine resin, urethane resin,
Organic fillers such as polyolefin resins, thixotropic agents such as Aerosil and organic bentonite, adhesion agents such as silane-based, aluminum-based or titanium-based coupling agents, defoaming of silicone oil and acrylic resin An agent, a dispersant, a nonionic surfactant for an antistatic agent, a pigment for coloring, and the like may be appropriately compounded. Further, the plastisol composition of the present invention, an epoxy resin and a curing agent thereof, a phenol resin, a thermosetting resin such as a urethane resin, and a photosensitive resin comprising an acrylic oligomer, an acrylic monomer, a photopolymerization initiator, and the like. Is also possible.

The plastisol composition of the present invention can be adjusted to an arbitrary fluidity by selecting the mixing ratio of the acrylic resin powder and the plasticizer, the selection of the additives and the amount of the additives depending on the intended use. It can be applied to the article by various coating methods such as screen printing, brush coating, roll coating, curtain coating and the like. Articles coated with the present invention are generally processed at a temperature of from 80 to 240C. The time required for gelling depends on the processing temperature, but is generally between 2 minutes and 2 hours. Hot air, infrared,
High-frequency heating and the like are common.

The plastisol composition of the present invention forms a partial film so that the solder does not adhere in a step such as soldering, and a peelable primary mask (stripable mask) used for peeling the film after soldering. The purpose of this product is to apply it to the spacer material of keyboard using flexible substrate, but it has good fluidity as sol and excellent storage stability, good moldability, good appearance of molded product, and safety. Because it is an acrylic resin-based plastisol composition with good heat resistance and heat resistance and easy control of product hardness, it can be impregnated or coated on a base material such as a car body protective film such as an automobile or a truck or cloth or paper, or a non-coated sheet. A single sheet obtained by applying and gelling on an adhesive surface and peeling it off, a glove or hollow body obtained by gelling and then peeling off after dip coating on a metal bill or pipe It can be widely used in the manufacture of such.

[0019]

The present invention will be described in more detail with reference to the following examples. Examples 1 and 2 and Comparative Examples 1 to 7
120 parts by weight of various plasticizers were mixed with 0 parts by weight to obtain a plastisol. Put this on a glass-epoxy substrate for about 20
It was applied with a bar coater to a thickness of 0 μm and heat-treated at 120 ° C. for 10 minutes to form a gel and a film. The appearance of the film (film formability) and the state of the plastisol after standing at room temperature for one week were observed. The results are shown in Table 1. In Table 1, the results of thermogravimetric analysis (temperature at which the weight decreases by 10% when heated at 5 ° C./min in air) are also shown as volatility.

As is clear from the results, the performance of the plastisol differs significantly depending on the type of the plasticizer used, and the phosphate ester plasticizer (CDP, TCP, RD)
P, BDP) are good results in film formability and storage stability. However, a plastisol using a phosphate ester plasticizer having a monomer structure such as CDP or TCP is gelled under the above-mentioned heat treatment conditions. It has been found that there is a drawback that the work environment is deteriorated, and the working environment is remarkably deteriorated. Furthermore, when these coatings are treated at higher temperatures, the plasticizer becomes more liable to evaporate, and such a heat-treated coating loses its flexibility and loses its flexibility. there were. In contrast,
When the condensed phosphate ester having a dimer structure such as RDP and BDP of the present invention is used as a plasticizer, the plasticizer itself becomes P
It has better thermal decomposition characteristics than MMA itself, and volatilizes only about several% or less under the conditions of normal film formation temperature and use temperature of 80 to 250 ° C. for several minutes to 2 hours. It was found that a film having stable characteristics could be formed as well as not being contaminated.

Examples 3 to 19 and Comparative Example 8 The following compounds (the unit of the compounding amount is parts by weight) were dispersed in a roll, followed by vacuum defoaming to prepare a plastisol. Table 2 shows the results of evaluating the storage stability of plastisols by comparing the viscosities of the plastisols after standing at 25 ° C. and 40 ° C. for 1 month each with the initial viscosities. The viscosity is 2 with an EHD type book field viscometer.
Value at a shear rate of 5 s ^{−1 at} 5 ° C. (unit: Pa)
・ S) was shown.

In a known example of an acrylic resin-based plastisol, the viscosity after leaving at room temperature for 8 days is 3 times or less of the initial viscosity (Japanese Patent Publication No.
No. 16177), no gelation at 40 ° C. for 10 days (JP-A-7-25953), little change in viscosity at 20 ° C. for 15 days (JP-A No. 8-165398), twice or less at 25 ° C. for 6 days (JP-A No. The present invention does not gel even at 40 ° C. for one month, and the increase in viscosity is less than three times that of the known plastisol. It is clear that the storage stability is much higher. In addition, when the monomer type phosphoric acid ester was used as a plasticizer (Comparative Example 8), it gelled after 1 month at 25 ° C. or 40 ° C. and showed no fluidity at all.

A glass-epoxy single-sided copper-clad laminate (no solder resist, hereinafter referred to as substrate 1) and a through-hole (0.9 mm in diameter) substrate (both sides of glass epoxy) were prepared by forming the plastisol of Example 9 and Comparative Example 8 in a copper foil pattern. The copper-clad laminate was formed with through-holes, and the periphery of the through-holes was formed with a solder resist. These were heat-treated at 130 ° C. for 10 minutes to gel. Using these test pieces, the practicality as a peelable primary mask (stripable mask) used for peeling it after soldering was evaluated by the following method. As a strippable mask, it is determined whether or not the gelled film can be peeled from the substrate and whether or not the gel film has a good peeling property even after the gel film is treated at a higher temperature.

(Table 1)

DOP: Dioctyl phthalate DBP: Dibutyl phthalate DOA: Dioctyl adipate O180A: Epoxidized oil (Kapox O180A, manufactured by Kao Corporation) Benzoflex 9-88: Dipropylene glycol dibenzoate CDP: Cresyl diphenyl phosphate TCP: Tricresyl phosphate Fate RDP: Resorcinol bisdiphenyl phosphate BDP: Bisphenol A bisdiphenyl phosphate Film formability ○: Form into a sheet form △: Sheet form but the film is brittle ×: Sheet form but very brittle ××: Not solidified (not gelled) *: Large amount of plasticizer seeping out of sheet Storage stability ○: No change in viscosity △: Increase in viscosity ×: Solidification volatility Temperature at which weight loss is 10% (5 in air) (Calculated from the TGA curve when the temperature is raised at ° C / min.)

(Table 2)

F301: Acrylic resin powder (epoxy-containing P
MMA) F303: Acrylic resin powder (modified PMMA) F320: Acrylic resin powder (PMMA) F325: Acrylic resin powder (PMMA) F340: Acrylic resin powder (MMA copolymer) RDP: Resorcinol bisdiphenyl phosphate TXP: Trixile Nil phosphate TCP: tricresyl phosphate 9-88: Benzoflex 9-88: dipropylene glycol dibenzoate triton A: calcium bicarbonate (manufactured by Shiroishi Calcium Co.) # 200: Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) Initial viscosity: 25 Initial viscosity at 25 ° C (unit: Pa · s) Storage at 25 ° C: viscosity at 25 ° C after storage at 25 ° C for 1 month 40 ° C storage: viscosity at 25 ° C after storage at 40 ° C for 1 month The results are shown in Table 3 below. . It is clear that the gel film obtained from the plastisol of the present invention has extremely excellent heat resistance and peelability.

(Table 3) a) Removability of through hole (substrate 2): ○ Gel film can be peeled without leaving all holes △ Gel film remains in through hole b) Untreated film peeling property (substrate 1) ○ Easily peeled from glass epoxy substrate Yes × Difficult to peel off and gel film cuts c) Heat treated film peelability (substrate 1) After heat treatment at 200 ° C for 30 minutes, it was cooled and evaluated for peelability ○ Easy to peel from glass epoxy substrate × Hard to peel and gel film cut d) Peeling property of film after soldering heat test (substrate 1) 260 ° C 5
Put on a solder bath for 2 seconds and evaluated the peelability after cooling. ○ Easy to peel off from glass epoxy substrate.

Examples 20 to 29 Plastisols were prepared according to the formulations shown in Tables 4 and 5. Here, all the compounding amounts are parts by weight. This plastisol was applied to a glass-epoxy substrate with a bar coater,
Heat treatment was performed at 0 ° C. for 10 minutes to form a gelled film. This was cut out to a width of 1 cm and a length of 6 cm and then peeled off to obtain a strip film. This sample was evaluated for mechanical properties using a tensile tester. The results are also shown in Tables 4 and 5. However, the results in Table 4 indicate that the tensile speed was 10 mm / min.
Table 5 shows that 50 mm / min. It is. here,
The effect of adding a hydroxy fatty acid ester (indicated as “added oil” in the table) to plastisol was confirmed. With these additions, it is possible to obtain a film with large elongation without drastically reducing the film strength. By adjusting the type and amount of the fatty acid ester, it was possible to widely change the film properties.

(Table 4)

(Table 5)

Additive oil A: glyceryl triacetyl ricino
Rate Additive oil B: Butyl ricinolate Additive oil C: Propylene glycol monoricinolate Additive oil D: Trimethylolpropane monoricinoleate Additive oil E: Sorbitan monoricinoleate Average film thickness Unit: μm Maximum load strength Unit: N / mm²  Breaking strength Unit: N / mm²  Maximum elongation Unit:% Elongation at break Unit:% Tensile modulus Unit: N / mm²

Incidentally, the plastisol of Example 24 was stored at 40 ° C., and the viscosity after storage for a predetermined time was measured at 25 ° C. (shear rate 10S ⁻¹ ). As a result, 18.5 Pa · s immediately after preparation.
Was 28.0P after 4 days of storage at 40 ° C.
After that, it was almost constant after that, and was stable at 28.5 Pa · s after 7 days, 29.0 Pa · s after 14 days, 28.6 Pa · s after 27 days, and 28.7 Pa · s after 50 days. Was.

Comparative Example 9 A mixture of 50 parts by weight of glyceryl triacetyl ricinoleate was dispersed in a roll with 70 parts by weight of an acrylic resin powder Zeon acrylic resin F320, followed by vacuum defoaming. This was bar-coated on a glass-epoxy substrate to a thickness of about 200 μm and heat-treated at 130 ° C. for 10 minutes.
It did not gel at all and did not become a solid film in paste form. That is, it was found that the hydroxy fatty acid ester as the additive of the present invention did not act as a plasticizer for the acrylic resin powder.

Example 30 160 parts by weight of BDP, 40 parts by weight of RDP, and spherical polyurethane particles (Artpearl HT-40) were used for 100 parts by weight of an acrylic resin powder Zeon acrylic resin F320.
A mixture obtained by adding 40 parts by weight (0T, manufactured by Negami Kogyo Co., Ltd.) and 2 parts by weight of Aerosil 200 was dispersed in a roll and defoamed in vacuo to obtain a plastisol. This was dip-coated on the grip portion (diameter 10 mm) of a SUS metal ladle, and heat-treated at 130 ° C. for 10 minutes to form a gel and a film. The film thickness is about 2.5m
m, it was hard to slip and became easy to grasp. The operation of scooping the molten solder with the ladle was repeated, but the temperature rise at the grip portion was small and the workability was improved. Further, even after repeated use, the film was tough and had no damage.

Example 31 In a keyboard (membrane keyboard) in which an electrode pattern is formed on two polyester (PET) substrates and the upper and lower electrodes are brought into contact by pressing, the upper and lower electrodes are not always in contact. A plastisol can be used as a spacer material for forming a space in the space. As a plastisol composition used for such a purpose, the following components were roll-dispersed and then vacuum defoamed to prepare.

Acrylic resin F320 (acrylic resin powder, manufactured by Zeon Corporation) 21 parts by weight Bisphenol A bisdiphenyl phosphate (plasticizer) 29 parts by weight QR9276 (urethane resin, manufactured by Asahi Denka) 32 parts by weight ED503 (epoxy resin diluted) 6.5 parts by weight Epicoat 828 (bisphenol A type epoxy resin) 7 parts by weight EH4070S (epoxy curing agent, manufactured by Asahi Denka Co., Ltd.) 4.5 parts by weight Aerosil # 200 (thixotropic agent, 0.1 parts by weight, calcium carbonate 2 parts by weight, phthalocyanine-based blue pigment 0.5 parts by weight, defoamer 1 part by weight These were applied by screen printing to a PET substrate on which a lower electrode was pattern-printed, and 150 ° C. 10 Heat treatment was performed to obtain a spacer material. This spacer material is made of conventional PVC
-A film could be formed under the same workability conditions as the DOP-based spacer, the adhesion of the substrate to PET was good, and substitution was possible. The conventional product had problems such as outflow of environmental hormones due to DOP at the time of disposal and generation of dioxin at the time of incineration of PVC.

[0038]

The plastisol according to the present invention has good fluidity as a sol, excellent storage stability, good moldability and good appearance, safety and heat resistance of a molded product (gelled product). An acrylic resin-based plastisol composition that can easily control the hardness of a product can be provided. Therefore, a peelable primary mask (stripping mask) used to partially form a coating so that solder does not adhere during soldering and other steps after soldering, and a keyboard spacer using a flexible substrate Application to materials and the like is possible. It can also be used as a sheet impregnated or covered with a base material such as a protective film or cloth or paper for automobiles and trucks, or as a single sheet obtained by applying and gelling on a non-adhesive surface and then peeling it off, metal bills and pipes. It can be widely used for the production of gloves, hollow bodies, etc. obtained by gelling and then peeling after dip coating.

[Brief description of the drawings]

FIG. 1 is a diagram of a thermogravimetric analysis of a condensed phosphate ester having a dimer structure used in the present invention and an ester having a conventional monomer structure. RDP of the present invention is resorcinol bis (diphenyl phosphate), BDP is bisphenol A bis (diphenyl phosphate),
Conventional CDP is cresyl diphenyl phosphate, T
CP is tricresyl phosphate.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshiya Tashiro 251 Suwa-cho, Hachioji-shi, Tokyo Asahi Chemical Laboratory Co., Ltd. (72) Inventor Yamada University 251 Suwa-cho, Hachioji-shi, Tokyo Asahi Chemical Laboratory Co., Ltd. F Term (reference) 4J002 BG061 BG071 CD171 CD191 EH137 EH157 EW046 FD010 FD026 FD140 GT00

Claims (3)

[Claims] 1. A plastisol composition comprising an acrylic resin-based plastisol composition comprising an acrylic resin-based powder and a plasticizer as main components, wherein a condensed phosphate ester is used as a plasticizer. 2. The condensed phosphoric ester of claim 1, wherein the resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate) and bisphenol A bis (dicresyl phosphate) are selected from the group consisting of: The plastisol composition according to claim 1, wherein said mixture is used. 3. The plastisol composition according to claim 1, wherein a hydroxy fatty acid ester is added.