JP3490769B2 - Acrylic sol composition for wallpaper - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an acrylic polymer,
Acrylic sol composition for wallpaper comprising plasticizer and filler
Regarding

[0002]

At present, commercially widely wallpaper plastisol composition used are those mainly composed of vinyl chloride sol composition obtained by a polyvinyl microparticles chloride filler is dispersed in a plasticizer , and the by further applications, this
Pigment vinyl chloride sol, thermal stabilizers, blowing agents, plus diluents, etc. are used.

[0003] In addition, the wallpaper is an interior material on the assumption the replacement, be sure to update the house of advance and reform,
It will be discarded. On the other hand, due to recent global environmental problems,
Vinyl chloride sol composition related products to generate hydrogen chloride gas when incinerated is said to destroy causative substance of the ozone layer, also not only has a causative agent of acid rain occurrence, chloride
When incinerating vinyl sol article in incinerators, significantly damaging the furnace, further the incineration has a problem that generate harmful substance called dioxin, especially vinyl chloride with more picture areas of opportunity for incineration sol The advent of a plastisol composition that does not have such drawbacks as an alternative to the composition is awaited.

Japanese Patent Publication No. 55-16177 discloses that
(1) tert. -Butyl acrylate, polymer of at least one monomer of C ₁ -C ₄ alkyl methacrylate or cyclohexyl methacrylate, or (2) at least one of the above monomers and C ₂ -C
₁₀ aliphatic alcohol _{methacrylates,} C 1 _{-C 10}
Acrylate of aliphatic alcohol, styrene and α-
A copolymer with at least one monomer selected from methylstyrene, having a glass transition temperature of 35 ° C. or higher, 400
Having an average molecular weight greater than
And an organic polymer component 100 parts by weight of 00Myuemu, plasticizer 30 to 1,000 parts by weight, inert fillers optionally up to 700 parts by weight, the plastisol composed of the usual additives
It is described . In addition, the organic polymer component may contain acrylic and / or up to about 3% by weight of free carboxyl, hydroxyl, epoxy or amino groups to improve the adhesion of the coating formed by the plastisol to the substrate. It is also suggested that a methacrylic monomer may be copolymerized. Further, it is a polymer composed of 50 parts by weight of butyl methacrylate and 50 parts by weight of methyl methacrylate, and is selected from polymer particles having an average particle size of 50 μm and dioctyl phthalate, dinonyl phthalate, didecyl phthalate, butyl cyclohexyl phthalate and the like. Plastisols with plasticizers are described .

[0005]

However, in the acrylic sol composition disclosed in Japanese Patent Publication No. 55-16177, a uniform composition type granular polymer is dispersed in a dialkyl phthalate type plasticizer such as dioctyl phthalate or diisononyl phthalate. However, acrylic polymer particles such as a 1: 1 copolymer of butylmethacrylate and methylmethacrylate dissolve quickly in the plasticizer and are fast, and the viscosity of the acrylic sol increases within a few minutes after mixing the two. Occurs, and coating becomes impossible, making it practically unusable.
Further, in order to delay the dissolution of the acrylic polymer particles in the plasticizer and improve the coating stability of the acrylic sol and the storage stability of the sol, a monomer component having low solubility in the plasticizer was copolymerized. A method using an acrylic polymer is conceivable, but the sol produced by this method causes various inconveniences when the plasticizer bleeds out on the coating film surface after film formation and is used as a coating film. That is, the sol using acrylic polymer particles having a uniform polymer structure does not generate hydrogen chloride gas when incinerated, but it has a low viscosity and is easy to apply, and does not thicken even after storage for several days. At present, there is no one having practical performance such as capable of forming a coating film having excellent performance. The object of the present invention is to produce a composition such as a vinyl chloride sol composition.
Use a polymer that does not generate hydrogen chloride gas when rejected
Dioctyl phthalate and diisononyl as plasticizers
Inexpensive and industrially advantageous dial such as phthalate
A new type that can withstand practical use by using a quiltphthalate plasticizer
An object is to provide a regular acrylic sol composition for wallpaper.

[0006]

The present inventors have SUMMARY OF THE INVENTION As a result of extensive investigations for the purpose of obtaining the acrylic sol composition obtained by solving the above problems, a core portion of the structure of the acrylic polymer fine particles used shell It was found that the above-mentioned problems can be solved by using a two-layer structure composed of parts and having a shell part made of a plasticizer-resistant polymer.

That is, the gist of the present invention is an acrylic sol composition containing acrylic polymer (A) fine particles, a plasticizer (B), and a filler (C) as main components,
The acrylic polymer (A) fine particles have a two-layer structure composed of a core portion and a shell portion, and the core portion has ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, sec. -Butyl methacrylate, ter
t. A homopolymer of at least one methacrylate selected from the group of butyl methacrylate, cyclohexyl methacrylate, ethylhexyl methacrylate or
An acrylic sol composition for wallpaper, comprising fine particles composed of a copolymer having an amount of methacrylate of 50% by weight or more .

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing fine particles of an acrylic polymer (A) used in the present invention, the structure of the obtained fine particles is 2
The method is not particularly limited as long as it is a method capable of forming a layer structure , but by using emulsion polymerization, fine particles of acrylic polymer (A) having a core / shell structure can be efficiently obtained.
It Recover acrylic polymer particles from polymer solution
Examples of the method include a spray drying method of a polymer solution, or a method of coagulating and drying by acid or salting out.
To be

The polymer ratio (% by weight) of the core portion and the shell portion of the fine particles of the acrylic polymer (A ) is core / shell = 2.
It is preferably 5/75 to 70/30 . The purpose of making the structure of the fine particles of the acrylic polymer (A) a core / shell structure is to provide the acrylic sol composition of the present invention with good storage stability and to obtain a gel formed from the acrylic sol composition.
This is to prevent the plasticizer from bleeding out with time of the polymerized film . The ratio of the core portion and the shell portion, if it also depends on the composition of the polymer forming them, with most plasticizer highly compatible polymer as the polymer for the core formation,
In the polymer ratio of the core portion and the shell portion (wt%) Core /
Shell = 25/75 made acrylic polymer (A) acrylic sol composition using fine particles, the balance between the performance of the gelling film formed from its storage stability and its acrylic sol composition becomes good. A gelled film formed from an acrylic sol composition prepared by using acrylic polymer particles having a lower core polymer ratio causes bleeding out of the plasticizer with time. Also, core / shell = 70/3
0 of the acrylic polymer (A) fine particles is intended lowest compatibility to plasticizers, but the polymer (A) gelled film formed from the acrylic sol composition containing fine particles excellent properties Have In the case of acrylic polymer particles in which the polymer ratio of the shell part is smaller than this, the coating of the shell component on the core part becomes poor, and the acrylic polymer particles with respect to the plasticizer are fine.
Since the solubility of the particles becomes high, the viscosity of the acrylic sol composition containing the polymer particles increases rapidly, and the storage stability due to the formation of gel becomes poor.

[0010] The structure of the core portion of the acrylic polymer (A) fine particles
As the polymer to be formed , ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate,
sec. -Butyl methacrylate, tert. - butyl methacrylate, cyclohexyl methacrylate, at least one methacrylate homopolymer or said methacrylates selected from the group consisting of ethylhexyl methacrylate
Over preparative amounts include 50 wt% or more of the copolymer.

[0011] The core component of the acrylic polymer (A) fine particles <br/> element used in the present invention is characterized in that high dialkyl phthalate plasticizer compatible, the methacrylate amount <br/> 50 The gelled film formed from the acrylic sol composition using less than wt% of the polymer is not preferable because the plasticizer bleeds out. The polymer that constitutes the core is a copolymer
As the copolymerizable monomer, the acrylate and methacrylate of C ₁ -C ₁₃ alcohol, acrylamide, methacrylamide, N-dimethylacrylamide, N-dimethylmethacrylamide, N-dimethylaminoethyl methacrylate, N-diethylaminoethyl methacrylate, Acrylonitrile, vinyl acetate, styrene, α-methylstyrene, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethylene glycol dimethacrylate, divinylbenzene, glycidyl methacrylate , allyl methacrylate and the like, these monomers used singly or two or Rukoto can.

Further , the acrylic polymer (A) fine particle shell
The polymer constituting the pole tip, methyl methacrylate, benzyl methacrylate, styrene, methacrylic acid, acrylic acid, itaconic acid, at least one monomer of the homopolymer or 該Mo selected from the group consisting of crotonic acid
Nomar amount include more than 50 wt% of the copolymer. Shell component of the acrylic polymer (A) fine particles used in the present invention, compatibility with dialkyl phthalate plasticizer is characterized by low <br/> Ikoto. The amount of the above monomer is not 50% by weight
Acrylic Weight having a shell portion formed by Mitsuru polymer
Acrylic sol composition comprising a polymer fine particle, diffusing into the acrylic polymer fine particles in the plasticizer, dissolved faster by increase in the viscosity of the acrylic sol composition coating defects and storage stability of <br/> poor Occur. Polymer copolymer constituting the shell portion
As the copolymerizable monomer, the acrylate and methacrylate of C ₁ -C ₁₃ alcohol, acrylamide, methacrylamide, N-dimethylacrylamide, N-dimethylmethacrylamide, N-dimethylaminoethyl methacrylate, N-diethylaminoethyl methacrylate, Acrylonitrile, vinyl acetate, styrene, α-methylstyrene, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethylene glycol dimethacrylate, divinylbenzene, glycidyl methacrylate, allyl methacrylate and the like, and these monomers Can use 1 type (s) or 2 or more types. The molecular weight of the polymer constituting the shell portion of the fine particles of the acrylic polymer (A) varies depending on the use, but the weight average molecular weight is 10,000 to
2,000,000 is preferred. The Tg of the polymer forming the shell portion is preferably room temperature or higher. Gel film which Tg of the polymer constituting the shell portion is formed from an acrylic sol composition comprising acrylic polymer fine particles <br/> element comprising less than room temperature,
It is not preferable because tackiness is easily expressed.

The particle size of the fine particles of the acrylic polymer (A) is
Preferably 0.1 to 100 μm, more preferably 5 to 3
It is in the range of 0 μm . The acrylic sol composition containing the fine particles of the acrylic polymer (A) having such a particle size has a good balance between the heat film-forming property and the storage stability. Acrylic sol composition comprising acrylic polymer fine particles the particle size is too large
Things, its diffusion into the acrylic polymer fine particles in the plasticizer upon heating deposition becomes poor, complete gelling of the gelling film formed from the acrylic sol composition does not occur. Also,
Acrylic sol composition comprising acrylic polymer fine particles the particle diameter is too small, the storage stability becomes insufficient. Servant
There, in the acrylic sol composition of the present invention, it is necessary to select the particle diameter of the acrylic polymer fine particles used in the required particle size in the sol.

The plasticizer (B) used in the present invention is a plasticizer composed of dialkyl phthalate compounds such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate and diundecyl phthalate. In particular, or dioctyl phthalate or diisononyl phthalate
Such a plasticizer is preferable because it is inexpensive and easily industrially available.

The acrylic polymer (A) fine particles and plasticizer
The mixing ratio of (B) is an acrylic polymer (A) fine particles 10
The ratio of 50 to 500 parts by weight with respect to 0 parts by weight,
It is preferable from the viewpoint of storage stability and coatability of the acrylic sol composition .

The filler (C) used in the present invention is calcium carbonate, baryta, clay, colloidal silica, mica powder, diatomaceous earth, kaolin, talc, bentonite, glass powder, sand, aluminum oxide and aluminum hydroxide, trihydrate. Examples include antimony oxide, titanium dioxide, carbon black, metallic soap, dyes and pigments. The amount of filler (C) used is
Preferably the acrylic polymer (A) 100 parts by weight of fine particles
Preferably set to a rate of 50 to 500 parts by weight against.

In addition to the above, the acrylic sol composition of the present invention can be made into an organosol by adding a solvent such as mineral terpene as a diluent. Further, various additives can be added depending on the purpose. For example, gelation is formed from an acrylic sol sets composition as the present invention
They are film adhesion promoters, leveling agents, anti-tack agents, release agents, defoamers, foaming agents, surfactants, ultraviolet absorbers, lubricants, flame retardants, and fragrances.

In order to apply the acrylic sol composition for wallpaper of the present invention to a wallpaper, the acrylic sol composition is applied to a base paper by a coating method such as a dip coating method, a knife coating method, a roll coating method and a curtain flow coating method. It suffices to apply the coating and gel the coating film at an appropriate gel forming temperature and treatment time . The gel formation temperature of the coating film is in the range of 70 to 260 ° C., and the treatment time is 30 seconds to
It is recommended that the range be 90 minutes. The acrylic sol composition is
Under this gelling condition, a uniform gelled film is formed and becomes a wallpaper. Further, the gelled film may be subjected to printing, embossing, foaming treatment or the like depending on the application.

[0019]

EXAMPLES The present invention will be described below with reference to examples. Na
All the parts in the examples are by weight parts.

Example 1 In a 5-liter four-necked flask, 1,251 parts of water and polyoxyethylene nonylphenyl ether (manufactured by Kao Corporation,
Product name Emulgen 910) 10.5 parts and potassium persulfate 0.75 parts are added, and isobutyl methacrylate 250 is added.
Parts were added, and the mixture was heated and polymerized at 70 ° C. for 5 hours while stirring at 180 rpm in a nitrogen atmosphere to form polymer particles to be the core part . Methyl methacrylate 578 was added to this reaction solution.
Part, 6 parts of methacrylic acid, and 5 parts of sodium dialkylsulfosuccinate (Kao Corporation, trade name Perex OTP) were added, and the mixture was heated and polymerized for 3 hours, then heated to 80 ° C. and held for 1 hour, and the shell portion was added. And the emulsion polymerization was completed. The minimum film forming temperature (MFT) of the obtained emulsion is 103 ° C, which is near the MFT of the methyl methacrylate polymer in the shell part, near 50 ° C of the MFT of the isobutyl methacrylate polymer alone in the core part, or near 80 ° C of the MFT of the copolymer. since it is not, the acrylic polymer fine particles in the emulsion such shown in Table 1 core /
It was confirmed to be a polymer particle having a two-layer structure of a core and a shell having a shell ratio. The obtained emulsion is pulverized using a spray dryer, and the average particle size is 10 μm.
Fine particles of acrylic polymer (A) were obtained. The acrylic polymer fine particles were observed through an electron microscope, the particle diameter 1μ
It was found that primary particles of m or less aggregated to form spherical particles having a particle diameter of about 10 μm.

[0021] Dioctyl phthalate 80 parts to 100 parts of the resulting acrylic polymer fine particles, calcium carbonate (Takehara Kagaku Kogyo Co., Ltd., trade name Neoraito SP) 50 parts, acrylic sol composition obtained by adding a mineral turpentine 10 parts Viscosity (25 ° C, E-type viscometer, manufactured by Tokyo Keiki Co., Ltd.) is 3,000c
It was ps. The acrylic sol composition was cooled to room temperature (25
The viscosity was 4,200 cps after being kept at (° C.) for 6 days. The storage stability of the acrylic sol composition thus obtained was practically sufficient. In addition, the acrylic sol composition was applied to flame-retardant paper with a knife coater at 100 μm.
Apply m thickness and heat at 200 ℃ for 30 seconds to make uniform gel.
Even when a film was formed and this gelled film was kept at 10 ° C. for 1 week, there was no bleeding of the plasticizer and the compatibility was good.
Further, it was confirmed that this gelled film had the properties as shown in Table 3 and was extremely excellent for wallpaper.

Example 2 Acrylic polymer fine particles shown in Table 1 were obtained in the same manner as in Example 1 except that the monomers shown in Table 1 were used, and the plasticizer was changed from dioctyl phthalate to diisononyl phthalate. In the same manner as in Example 1, an acrylic sol composition was prepared, a gel film was formed using this acrylic sol composition , and the evaluation results were shown in Table 3.

[0023] Using the monomers shown in (Example 3) Table 1, to obtain an acrylic polymer fine particles in the same manner as in Example 1, the acrylic polymer fine
While preparing an acrylic sol composition using particles ,
Make a gelled film with this acrylic sol composition
The evaluation results of the chemical film are shown in Table 3.

( Comparative Examples 1 and 2 ) Using the monomers shown in Table 1, by the same procedure as in Example 1, the acrylic polymer having the same core and shell polymer compositions as shown in Table 1 and having no layer structure was prepared. Get fine particles,
An acrylic sol composition was prepared in the same manner as in Example 1 using the polymer particles, and the gel film obtained using the sol composition was evaluated. The results are shown in Table 3. It was In Comparative Example 1 , the fine particles of the acrylic polymer were dissolved in the plasticizer , the viscosity of the acrylic sol composition increased, and the sol composition gelled after 2 days. The viscosity and storage stability of the acrylic sol composition obtained in Comparative Example 2 were good, but when the gelled film of this acrylic sol composition was left to stand, the plasticizer separated and the gel
The plasticizer bleed out on the surface of the chemical film and could not be used as wallpaper.

[0025] Using the monomers shown in (Example 4-5) Table 2, to obtain an average particle size acrylic polymer fine particles such as shown in Table 2 in the same manner as in Example 1, the acrylic polymer fine particles Acrylic sol composition is prepared by using this sol composition
A gelled film was formed by using the gelled film, and the results of evaluation of this gelled film are shown in Table 3.

Example 6 Emulsion polymerization was carried out in the same manner as in Example 1 to obtain an emulsion containing fine particles of acrylic polymer having a core / shell structure. 1,000 parts of the obtained emulsion was put into 1,000 parts of a 2% aqueous solution of aluminum chloride heated to 90 ° C. to salt out and coagulate the acrylic polymer. The solidified acrylic polymer was filtered using a # 300 mesh sieve, washed with water, and then dried in a hot air oven at 70 ° C. for 10 hours to obtain fine acrylic polymer particles. The obtained acrylic polymer microparticles had an average particle diameter of 25 μm. This acrylic heavy
An acrylic sol composition was prepared by using the combined fine particles in the same manner as in Example 1, a gelled film was formed from this sol composition , and the evaluation results were shown in Table 3.

Example 7 In a 5-liter four-necked flask, 1,251 parts of water and polyoxyethylene nonylphenyl ether ( commercially available from Kao Corporation, commercial
Product name Emulgen 910) 14.5 parts and potassium persulfate 1.0 part were added, followed by ethyl methacrylate 125.
Part, methyl methacrylate 50 parts, butyl acrylate 75 parts monomer mixture in polyoxyethylene nonyl phenyl ether (Kao Corporation, trade name Emulgen 905)
After adding 4.0 parts, in a nitrogen atmosphere,
5 hours at 70 ° C. with stirring at rpm, heated polymerization, co
Polymer particles to be part A were formed. Next, a monomer mixture obtained by adding 3 parts of sodium dialkylsulfosuccinate (Kao Corporation, trade name Perex OTP) to 300 parts of methyl methacrylate was placed in a flask and heat-polymerized for 3 hours to form one layer of shell part on the outer periphery of the core part. Eyes formed. Furthermore, 160 parts of methyl methacrylate, 4 parts of methacrylic acid and 4 parts of methacrylic acid and 2 parts of sodium dialkylsulfosuccinate (Kao Corporation, trade name Perex OTP) were added to the mixture, and the mixture was heated and polymerized for 2 hours. The temperature was maintained for 1 hour, and a second shell part layer was formed on the outer periphery of the first shell part layer of the acrylic polymer particles. The resulting emulsion with a spray drier was to obtain an acrylic polymer fine particles <br/>, average particle diameter of the polymer fine particles 15μ
It was m. Using the acrylic polymer particles, an acrylic sol composition was prepared in the same manner as in Example 1, a gelled film was formed using this acrylic sol composition, and the results of evaluation of the performance thereof are shown in Tables 2 and 3. It was shown to.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

[0031]

As described above in detail, the acrylic sol composition for wallpaper of the present invention does not have a large thickening property, has excellent coatability, and has extremely good storage stability. . Moreover, the wallpaper made using this acrylic sol composition does not bleed out the plasticizer on the upper surface of the wallpaper even if it is stored for a long period of time . Also, the wallpaper is not such as the occurrence of which hydrogen chloride was incinerated, the possibility of environmental pollution is extremely small.

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 33/06-33/12 C08L 51/06 C08F 265/06

Claims (4)

(57) [Claims] 1. An acrylic sol composition comprising acrylic polymer (A) fine particles, a plasticizer (B) and a filler (C) as main components, wherein the acrylic polymer (A) fine particles form a core portion. It has a two-layer structure composed of a shell part, and the core part has ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, sec. -Butyl methacrylate, tert. -A homopolymer of at least one methacrylate selected from the group of butyl methacrylate, cyclohexyl methacrylate, and ethylhexyl methacrylate, or the amount of the methacrylate is 50% by weight or more.
An acrylic sol composition for wallpaper, characterized in that it is fine particles composed of a copolymer . 2. The polymer ratio (% by weight) of the core part and the shell part of the fine particles of the acrylic polymer (A) is core / shell =
It is 25 / 75-70 / 30, The acrylic sol composition for wallpapers of Claim 1 characterized by the above-mentioned. 3. The shell part is methyl methacrylate or benzene.
Dilmethacrylate, styrene, methacrylic acid, acrylic
Less selected from the group of acid, itaconic acid, crotonic acid
Both are homopolymers of one kind of monomer or the amount of the monomer is
The acrylic sol composition for wallpaper according to claim 1 or 2, characterized in that the acrylic sol composition comprises 50% by weight or more of a copolymer . Wherein the plasticizer (B) is wallpaper acrylic sol composition according to any one of claims 1 to 3, wherein the dialkyl phthalate compound.