JPS62288668A - Aqueous primer conditioner - Google Patents

Abstract

PURPOSE:The titled conditioner having improved blotting preventing properties, alkali sealing properties, adhesivity to top coating compound, etc., comprising acrylic polymer emulsion which is stabilized with protective colloid of PVA type having <=specific polymerization degree and has specific particle diameter as a main component. CONSTITUTION:The aimed composition which is stabilized with protective colloid of PVA type (preferably acetoacetylated PVA) having <=500 average polymerization degree and has 20-100nm average particle diameter as a main component. An acrylic polymer emulsion obtained by subjecting a (meth)acrylic acid ester monomer containing 1-12C alkyl group and optionally a copo lymerizable monomer to emulsion polymerization is preferable as the acrylic polymer emulsion.

Description

[Detailed Description of the Invention] When paint is directly applied to calcium silicate boards (hereinafter referred to as silica boards), ALC boards, cement mortar surfaces, slate boards, wood surfaces, etc., peeling or deterioration of the paint film may occur. There are many.

If the material of the base material to be painted is brittle or the surface of the base is chalked, peeling of the paint film will occur even if paint is applied on top of it to form a paint film. In such cases, it is necessary to harden the base.

Furthermore, if an emulsion paint is applied to a highly absorbent substrate, the water will be absorbed before a film is formed, and the paint will not form and will peel off. In this case, it is necessary to perform suction prevention treatment.

Furthermore, if the base is a slate board or a new cement mortar surface, the alkali contained therein will ooze out to the surface over time and attack the paint film, causing deterioration and peeling. In this case, it is necessary to use a barrier to prevent alkali.

Also, even if the base is hard and does not absorb, depending on the compatibility with the top coat, the adhesion may be poor and it may peel off. In such cases, it is necessary to perform adhesion treatment. The material used to treat the base in this way is base: J8 preparation.

The present invention is suitable for use on brittle and highly absorbent surfaces such as silica plates, which are considered to be the most difficult of these, as well as surfaces with chalking, such as old mortar surfaces and surfaces where previously applied coatings have aged. The object of the present invention is to provide an aqueous base conditioner that is highly effective in solidifying absorbent substrates such as. Of course, it has sufficient performance as a general base conditioner, such as providing barrier properties and improving adhesion.

[Prior Art and Its Disadvantages] Solvent-based base conditioners have conventionally been used to solve these problems. However, since solvent-based base conditioners have a strong odor and are toxic and flammable, there is currently a demand for the development of water-based base conditioners from the viewpoints of pollution prevention, safety, and handling.

Aqueous solutions of water-soluble resins such as polyvinyl alcohol are
Although it has good permeability to the substrate, it has the fatal drawback of not being water resistant because it is originally water soluble.

As a result, the top coated film may also be washed away by rainwater, resulting in poor adhesion to the top coat. In addition, like solvent-based resins, when the degree of polymerization is increased to improve the performance of the resin, or when the content of the resin is increased to improve drying properties, the viscosity increases and workability deteriorates significantly.

In addition, ordinary synthetic resin emulsions obtained by emulsion polymerization in the presence of emulsifiers and protective colloids can be replaced with lower viscosity ones even if they have a high degree of polymerization or high concentration, so they are easier to work with than solvent-based or water-soluble resins. However, since the particle size is as large as 100 to 10 G0 nm, it cannot penetrate into the micropores of an absorbent and brittle substrate that has micropores, and is not effective in solidifying the base. Further, there are drawbacks such as poor water resistance, adhesion to the substrate, and corrosion resistance of the coating film formed on the substrate surface due to the influence of the emulsifier and protective colloid used.

Depending on the manufacturing method, synthetic resin emulsions can also be made with extremely small particle sizes. For example, by emulsion copolymerizing an unsaturated carboxylic acid and partially neutralizing the resulting emulsion with an alkali, it is possible to partially dissolve the emulsion and obtain an emulsion with a fine particle size of 50 to 1100 nm. However, the fine particle emulsion obtained in this way has the disadvantage of poor water resistance because it is similar to a water-soluble resin.
Although they are called fine particles, this is probably because the particles are swollen by the alkali, but they have almost no permeability to highly absorbent substrates. Therefore, after application to a substrate and drying, it does not exhibit a solidifying effect as confirmed by a peel test.

Furthermore, by using a large amount of emulsifiers with strong emulsifying power such as anionic surfactants, 50 to 100 n11
An emulsion with a fine particle size can be obtained.

However, the microparticle emulsion obtained in this way has drawbacks such as poor water resistance due to the presence of a large amount of emulsifier, and the weak binding force between the emulsifier and resin, but it is not extremely absorbent like a silica plate. For extremely brittle substrates,
There is a drawback that only the emulsifier aqueous solution is absorbed first and only the resin remains, and the remaining resin aggregates with each other and remains on the surface of the substrate, and does not penetrate into the interior and therefore does not have a solidifying effect.

[Means for Solving the Problem] In view of the above problems, the present inventors have developed a particle size 110 using polyvinyl alcohol resin, which is said to undergo graft polymerization among water-soluble polymeric protective colloids, as an emulsifier.
If a fine particle emulsion with a particle size of 0n or less is changed, the protective colloid is bound to the emulsion particles, so only the protective colloid aqueous solution can be prevented from being sucked into the substrate first, and the resin fine particles can penetrate deep into the substrate, improving the base conditioning effect. We thought that this would be possible, and conducted various studies using acrylic monomers that form polymers with excellent water resistance. However, it is extremely difficult to emulsion polymerize acrylic monomers using polyvinyl alcohol-based protective colloids, and there is a method that uses a large amount of chain transfer agent, but this method results in extremely large particle sizes of 100 to 11,000 nm. However, an emulsion with fine particle size could not be obtained.

As a result of further research, the present inventors found that a specific Fl'f
When an acrylic monomer is emulsion-polymerized using polyvinyl alcohol-based protective colloid from synthetic leather as an emulsifier, an extremely fine acrylic polymer emulsion with a particle size of 20 to 100 nm is obtained, and a base conditioner containing this as a main component is produced. By preparing and applying it to an absorbent substrate, it was found that all of the above problems were solved, and the present invention was completed.

c. Detailed Description of the Present Invention] That is, the present invention provides an aqueous base preparation whose main component is an acrylic polymer emulsion with an average particle size of 20 to 1100 nm stabilized with a polyvinyl alcohol protective colloid having an average degree of polymerization of 500 or less. It is a drug.

The acrylic polymer emulsion having a particle size of 20 to 1100 nm used in the present invention is obtained by emulsion polymerization of the following acrylic monomers together with a copolymerizable monomer if desired. That is, the acrylic monomers include acrylic acid alkyl esters in which the alkyl group has 1 to 12 carbon atoms, and methacrylic acid alkyl esters in which the alkyl group has 1 to 12 carbon atoms.

Monomers copolymerizable with these include aromatic vinyl compounds such as styrene and methylstyrene, vinyl acetate,
Vinyl esters such as vinyl esters of saturated carboxylic acids branched at the alpha position, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid, acrylonitrile, acrylamide, N-methylolacrylamide, glycidyl methacrylate, hydroxyacrylate, ethylene dimethacrylate and so on.

Particularly preferred monomer combinations include butyl acrylate-methyl methacrylate-acrylic acid, butyl acrylate-2-ethylhexyl acrylate-styrene-acrylic acid, and the like.

Further, when an unsaturated carboxylic acid is used in combination, not only stability is improved but also the particle size is reduced.

Polyvinyl alcohol protective colloids used for emulsion polymerization of acrylic monomers together with copolymerizable monomers, if desired, include polyvinyl alcohol, acetoacetylated polyvinyl alcohol, butyralized polyvinyl alcohol, thiolated polyvinyl alcohol, etc. Among these, the degree of polymerization of polyvinyl alcohol is 500 or less. If the degree of polymerization exceeds 500, fine particle diameter cannot be obtained, and therefore the desired acrylic polymer emulsion cannot be obtained.

There is no particular need to limit the degree of saponification of polyvinyl alcohol. Therefore, it may be a completely saponified product or a partially saponified product.

Among the polyvinyl alcohol-based protective colloids mentioned above, especially when acetoacetylated polyvinyl alcohol is used,
You can use an acrylic polymer emulsion with fine particle size that has even better water resistance.

Further, an anionic surfactant and a nonionic surfactant can be used in combination with the polyvinyl alcohol protective colloid. Particularly suitable are nonionic surfactants, and among them polyoxyethylene nonylphenol ether and block polymers of polyoxyethylene and polyoxypropylene, those having an IILB of about 15 to 18 are particularly suitable.

In addition, as a polymerization initiator for emulsion polymerization of an acrylic monomer together with a copolymerizable monomer if desired, peroxides such as potassium persulfate and ammonium persulfate, and redox polymerization initiators in combination with these and a reducing agent are used. agent is used. Also preferably used is a redox polymerization initiator containing hydrogen peroxide and L-ascorbic acid.

The aqueous base conditioner of the present invention, which is mainly composed of an acrylic polymer emulsion with a particle size of 220-100 nm, has a concentration of 1
A range of 50 to 30 weight 96, especially 5 to 30 weight 96, is suitable from the viewpoint of workability, permeability, etc. when coating on a base material. If necessary, additives such as pigments, dyes, fillers, preservatives, and fungicides can be added.

The application method can be appropriately adopted such as spray, roller, or brush.

[Effects] The aqueous base 2I conditioner of the present invention not only has excellent performance as a base 2I conditioner, such as suction prevention properties, alkal sealing properties, and adhesion with top coat paints, but also has superior properties compared to conventional water-based base 2I conditioners. Base: A'! It has the effect of solidifying absorbent substrates such as silica boards and chalked surfaces, which are difficult to prepare with Il agents, so it is also possible to apply a top coat or affix a waterproof sheet to such absorbent substrates. It became possible to do.

Next, a method for polymerizing an acrylic polymer emulsion having an average particle diameter of 20 to 1100 nm to be used as the main component of the aqueous base conditioner in the present invention will be described.

That is, using the polyvinyl alcohol-based protective colloid with an average degree of polymerization of 500 or less, the acrylic monomer is emulsion polymerized with a copolymerizable monomer if desired, and the method for charging the monomers is as follows: A batch method or a continuous charging method may be used, or a method may be used in which a portion is first charged and polymerized, and then the remaining portion is continuously charged. The monomers to be charged continuously may be charged as they are, but the monomers may be charged as an emulsion using water and an emulsifier. Further, depending on the type of polymerization initiator, high temperature polymerization or redox polymerization may be used.

According to such a polymerization method, an acrylic polymer emulsion with a fine particle size and a concentration of about 20% by weight or less can be obtained, but in order to further obtain a concentration of 20ffi 0% or more, for example, about 50% by weight, chain transfer is necessary. agent must be present. This is because the affinity between the acrylic monomer and the polyvinyl alcohol protective colloid is poor, and in order to obtain a highly concentrated emulsion, the polymerization reaction will not proceed unless a chain transfer agent is added to improve the affinity.

Chain transfer agents used include alcohols such as methanol and ethanol, carbon tetrachloride, monochloromethane, dichloromethane, dichloroethane, chloroform, trichloroethylene, perchloroethylene, and tertiary chloride.
Halogen substituted hydrocarbons having 1 to 8 carbon atoms such as butyl chloride, 2 to 8 carbon atoms such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, acetaldehyde, propionaldehyde, n-butyraldehyde, furfural, benzaldehyde, etc. Carbonyls containing atoms, dodecyl mercaptan,
lauryl mercaptan, normal butyl mercaptan,
One or more mercaptans such as 2-ethylhexylthioglycolate, trichlorobromomethane, and octyl thioglycolate can be used.

The ratio of methanol used varies depending on the type of chain transfer agent, so it cannot be specified uniformly, but to explain a typical example, when methanol is used, 5 to 5
15% by weight, 0.0 when using acetaldehyde
1 to 2% by weight is suitable.

(Example) Next, the present invention will be explained with reference to Examples and Comparative Examples.

Example 1 An acrylic polymer emulsion with a fine particle size using a polyvinyl alcohol protective colloid was prepared according to the following formulation and polymerization conditions, and this was then diluted with water to prepare an aqueous base conditioner.

(Formulation) (Parts by weight) Butyl acrylate 57 Methyl methacrylate 57 Acrylic acid
2.0 polyvinyl alcohol (saponification degree 88 mol%, average polymerization degree methanol 1B deionized water
260 10% hydrogen peroxide aqueous solution
4.01O% L-ascorbic acid aqueous solution
4.010% ammonia water Appropriate amount (polymerization conditions) Polymerization temperature 5O-1i 0℃ initial polymerization
1O% dropping time of monomer
3 hours reaction time 4 hours (properties of acrylic polymer emulsion) Concentration
32.0% by weight Average particle diameter 35nm pH 7.5 Viscosity 1150c
P (properties of water-based base conditioner) Concentration 20.0f
f1% viscosity 5G
>cP (Others are the same as the above acrylic polymer emulsion) Example 2 An acrylic polymer emulsion with a fine particle size using a polyvinyl alcohol protective colloid was prepared according to the following recipe and polymerization conditions, and then this was diluted with water. and used as an aqueous base conditioner.

(Formulation) (Parts by weight) Butyl acrylate 57 Methyl methacrylate 37 Styrene
20 acrylic acid
3.0 Acetoacetylated polyvinyl alcohol (degree of saponification 99 mol%, average degree of polymerization 500, degree of acetylation 5 mol%) 113 Methanol
1B deionized water
2401O% hydrogen peroxide aqueous solution 5
．． 010% L-ascorbic acid aqueous solution 5.01
0% ammonia water Appropriate amount (polymerization conditions) Polymerization temperature 50~BO℃ initial polymerization
10% dropping time of single polymer
3 hours reaction time 4 hours (properties of acrylic polymer emulsion) Concentration
31.5% by weight Average particle diameter 70nm, l(7.5 Viscosity 800c
P (properties of water-based base conditioner) Concentration 20.0f
fi amount 96 viscosity
50>cP (Others are the same as the above acrylic polymer emulsion) Example 3 An acrylic polymer emulsion with a fine particle size using a polyvinyl alcohol protective colloid was prepared using the following recipe and polymerization conditions, and then this was mixed with water. It was diluted to make an aqueous base conditioner.

(Formulation) (Parts by weight) Butyl acrylate 57 Methyl methacrylate 57 Acrylic acid
2.0 polyvinyl alcohol (saponification degree 88 mol%, average polymerization degree polyoxyethylene nonyl phenol ether (COf: L 30 mol)) 4.0 ethanol
16 deionized water
1501O% hydrogen peroxide aqueous solution
4.010% L-ascorbic acid aqueous solution 4.010% ammonia water Appropriate amount (polymerization conditions) Polymerization temperature 50-b Initial polymerization 1096 drops of monopolymer Time 3 hours Reaction time 4 hours (Properties of acrylic polymer emulsion) Concentration
45.0% by weight Average particle diameter 55nm pH 7.5 Viscosity 5000c
P (Properties of water-based base 21 preparation) N1::1 degree
20, Q m Q 1'6 viscosity
50>cP (Others are the same as the above acrylic polymer emulsion) Example 4 An acrylic polymer emulsion with a fine particle size using a polyvinyl alcohol protective colloid was prepared using the following recipe and polymerization conditions, and then this was mixed with water. It was diluted to make an aqueous base conditioner.

(Formulation) (Parts by weight) Butyl acrylate 57 Methyl methacrylate 57 Acrylic acid
2.0 Polyvinyl alcohol (saponification degree 88 mol%, average polymerization degree methanol 16 deionized water
26012% potassium persulfate
5.0 (Polymerization conditions) Polymerization temperature 70~b Initial polymerization lθ% dropping time of monopolymer
3 hours reaction time 4 hours (properties of acrylic polymer emulsion) Concentration
32.0% by weight Average particle diameter 50nm pH 7.5 Viscosity 300
eP (aqueous base: properties of A precipitator) Concentration: 20.0% by weight Viscosity: 50>
cf' (Others are the same as the above acrylic polymer emulsion) Example 5 Using the following recipe and polymerization conditions, an acrylic polymer emulsion with a fine particle size using a polyvinyl alcohol protective colloid was prepared, and this was used as it was to prepare an aqueous base. It was used as a drug.

(Formulation) (Parts by weight) Butyl acrylate 20 Methyl methacrylate 20 Acrylic acid
1.0 polyvinyl alcohol (degree of saponification 88 mol%, average degree of polymerization 300) t.

Deionized water 24012% ammonium persulfate 5.0 (polymerization conditions) Polymerization temperature 70-b Initial polymerization 1096 dropping time of monopolymer 2 hours 30 minutes Reaction time
3 hours 30 minutes (properties of acrylic polymer emulsion) 4 degrees 20
,0wt% average particle diameter 80nI111
) H7.5 Viscosity 100
Comparative Example 1 Same as the acrylic polymer emulsion described in cP (Properties of aqueous base conditioner) An acrylic polymer emulsion using a polyvinyl alcohol protective colloid was prepared using the following recipe and polymerization conditions, and then this was mixed with water. It was diluted to prepare a comparative aqueous base conditioner.

(Formulation) (Parts by weight) Butyl acrylate 57 Methyl methacrylate 57 Acrylic acid
2.0 Acetoacetylated polyvinyl alcohol (degree of saponification 99 mol%, average degree of polymerization 1000, degree of acetoacetylation 5 mol 96) 16 Methanol
40 deionized water
2501O% hydrogen peroxide aqueous solution 5
．． 010% L-ascorbic acid aqueous solution 5.010% ammonia water Appropriate amount (polymerization conditions) Polymerization temperature 50~b Initial polymerization 10% dropping time of monopolymer
3 hours reaction time 4 hours (properties of acrylic polymer emulsion) Concentration
30.0% by weight Average particle diameter 200nmp H7.5 Dryness 3000
cP (properties of aqueous base conditioner) Concentration: 20.0% by weight Viscosity: 50
>cP (Others are the same as the above acrylic polymer emulsion) Comparative Example 2 An acrylic emulsion containing a carboxyl group was prepared according to the following recipe and polymerization conditions, and this was partially dissolved in aqueous ammonia to form an acrylic emulsion with a fine particle size. A polymer emulsion was prepared and diluted with water to prepare a comparative aqueous base conditioner.

(Polymerization recipe) (Parts by weight) Butyl acrylate 90 Methyl methacrylate 60 2-hydroxyethyl methacrylate 6.7 Methacrylic acid
9.4 Octyl thioglycolate (chain transfer agent) 8.0 Sodium lauryl sulfate 2.5 Polyoxyethylene nonyl phenol ether 2.0 Deionized water 3001296 Potassium persulfate aqueous solution 5.0 (micronization formulation) Polymerization using the above formulation Emulsion made entirely of ion-exchanged water
210 parts by weight 10% ammonia water
36.5 parts by weight (polymerization conditions) Polymerization temperature 70~b Initial polymerization 1O% dropping time of monopolymer
3 hours reaction time 4 hours (atomization conditions) Add deionized water to the emulsion and raise the temperature to 90°C.
Neutralize with ammonia water and mature for 1 hour.

(Properties of acrylic polymer emulsion) Concentration
24.6% by weight Average particle diameter 30nm pH9 Viscosity 15
0cP (properties of aqueous base conditioner) Concentration 20.
0wt% viscosity
50>cP (Others are the same as the above acrylic polymer emulsion) Comparative Example 3 Using the following formulation and polymerization conditions, an acrylic polymer emulsion with a fine particle size using a large amount of a surfactant emulsifier was made, and then this was It was diluted with water to provide a comparative aqueous base conditioner.

(Formulation) (Parts by weight) Butyl acrylate 45 Methyl methacrylate 55 Acrylic acid
2.0 Sodium lauryl sulfate
8.0 Deionized water 1751
2% ammonium persulfate aqueous solution 2510% ammonia water Appropriate amount (polymerization conditions) Polymerization temperature 70-80°C Dropletization time of emulsified monomer 5 hours Reaction time 8 hours (properties of acrylic polymer emulsion) Concentration
35.0% by weight Average particle diameter 30nm pH8 Viscosity 5000c
P (properties of aqueous base conditioner) Concentration: 20.0% by weight Viscosity: 50
>cP (Others are the same as the above acrylic polymer emulsion) Comparative Example 4 DAN tile sealer (solvent-soluble base conditioner manufactured by Nippon Paint ■: A degree 30ffi amount %) was mixed with toluene at a concentration of 2.
It was diluted to 0.0 weight 96 and used as a comparative base conditioner.

For reference, specifications regarding the aqueous base conditioners of Examples 1 to 5 and Comparative Examples 1 to 3 are summarized in Table 1.

Comparison test 1 (base adjustment characteristics for light silica board) Vertical 25co+x Width 12.5clllX Thickness 8Ia1
1 lightweight silica board (asbestos fiber contamination rate 15% by weight, specific gravity 0
．． 8) A sample was prepared, and the aqueous base conditioner of Examples 1 to 5 and Comparative Examples 1 to 3 and the solvent-soluble base conditioner of Comparative Example 4 were applied to it, and the solidification of the silica board surface and the alkali Sealing performance and adhesion with top coat paint were investigated.

The results were as shown in Table 2.

The test method was as follows: 150 g/rrr of base conditioner was applied to the surface of the silica board sample, and after drying at room temperature for 10 minutes, the surface layer was subjected to a peel test using cellophane tape.

08 The surface layer was sufficiently solidified without peeling.

68 The surface layer is slightly peeled off and solidification is not sufficient.

×: The surface layer is almost peeled off and is not solidified.

(Alkali sealability) Both sides of the silica plate sample were coated with a base conditioner at a ratio of 150 g/g, and after drying at room temperature for one day, the sides were sealed with paraffin wax and the ion of p14 [f, 8 was coated. The sample was immersed in a glass vat filled with 500 ml of exchanged water for 24 hours, and the pH was measured.

○: Good alkali sealing property (pH after immersion is 6.8 to 7)
．． 5) Δ: Slightly poor alkali sealing property (pH after immersion is 7.5)
~8.0) ×: Poor alkali sealing property (pH after immersion is 8.0 to 9)
．． 0) (Two-coat paint adhesion) Normal adhesion Apply 150 g/day of base conditioner to the surface of the silica board sample, dry at room temperature for 1 day, and then apply Nitsupe Water-Based New Wide (Rohon Paint ■ for internal and external use). Dry emulsion paint W2O
After coating at a concentration of 0 g/g and drying at room temperature for 5 days, the surface was cross-cut and a peel test using cellophane tape was performed.

Water resistant adhesion Apply the emulsion paint in the same manner as above and leave it for 5 minutes at room temperature.
After drying for 0 minutes, it was immersed in water for 1 day, and after drying at room temperature for 20 minutes, the surface was cross-cut and a peel test using cellophane tape was performed.

0: Peeling is less than 10% mainly at the cross-cut portion.

Δ: Peeling around the cross cut part is lO~5096° ×: Peeling exceeds 50% mainly at the cross-cut portion.

Comparative Test 2 (Substrate adjustment characteristics for chalked surfaces) Polyvinyl acetate emulsion paint was applied to a slate board, exposed to heat outdoors, and after confirming sufficient chalking, the board was cut into 25 cm (vertical) x 12.5 cm (horizontal). Chalking plate samples were prepared, and the water-based base conditioners of Examples 1 to 5 and Comparative Examples 1 to 3 and the solvent-soluble base conditioner of Comparative Example 4 were applied to the samples, and the hardening properties of the chalked surface and the topcoat coating were evaluated. The adhesion was investigated.

The results were as shown in Table 3.

(Solidification of Chalking Surface) A base conditioner was applied at 150 g/day to the surface of a chalking plate sample, and after drying at room temperature for one day, a peeling test was performed on the surface layer using cellophane tape.

O: The surface layer is sufficiently solidified without peeling. 68 The surface layer is slightly peeled off and solidification is not sufficient.

X: The surface layer was almost peeled off and was not solidified.

(Adhesion of top coat paint) 150 g/day of base conditioner was applied to the surface of the fabric adhesion chalk plate sample, and after drying at room temperature for 1 day, Nippelk New Wide (Nippel New Wide (Nimulsion paint for interior and exterior use made by Nippon Paint)) was applied. Drying tube ff1200g/rr? After drying at room temperature for 5 days, a peel test was performed using a goblin surface test.

Water resistant adhesion Apply the emulsion paint in the same manner as above and leave it for 5 minutes at room temperature.
After drying for one day, it was immersed in water for one day, dried for two days at room temperature, and then subjected to a peel test using a goblin surface test.

O: Peeling is less than 1096.

Δ: Peeling is 10% to 50%.

×: Peeling exceeds 50%.

Procedural amendment stamp button July 8, 1985 1 Display of the case 1986 Patent Application No. 132040 2 Name of the invention Aqueous base conditioner 3 Person making the arrest 4 Agent 540 Address 2 Tanimachi, Higashi-ku, Osaka City 37-chome NS Building
・Object of 5 amendments by 1 and 1 other person (1) Contents of amendment in column 6 of “Detailed Description of the Invention” of the specification (1) Change “Detailed Description of the Invention” on page 7, line 51 of the specification to “Detailed Description of the Invention”
amended to ``Composition of the invention''.

("Hydroxyacrylate" on page 21-48, lines 6-7 is corrected to "2-hydroxyalkyl acrylate."

(3) "Ethylene dimethacrylate" in line 7 on page 8 is corrected to "ethylene glycol dimethacrylate."

(4) 6 lines on page 15, 1 line on page 17, 5 lines from the bottom on page 18,
r 50 > cPJ on page 20, line 7, page 23, line 8, page 25, line 11, and the bottom two lines of page 2B are corrected to r 50 cP > J.

(5) r ``25'' on page 26, line 6 5. Correct with O.J.

(6) "Table 1" on page 32 is amended as follows.

Claims (1)

[Claims] 1. Average particle size 20-100n stabilized with polyvinyl alcohol protective colloid with average degree of polymerization of 500 or less
An aqueous base conditioner whose main component is an acrylic polymer emulsion.