JPS5811445B2 - Emulsion composition containing petroleum-based hydrocarbon resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an emulsion composition containing a petroleum-based hydrocarbon resin.

The emulsion composition of the present invention is useful, for example, as a coating composition and a waterproofing agent for paper.

The petroleum-based hydrocarbon resin as used in the present invention refers to a hydrocarbon resin obtained by polymerizing unsaturated moieties in by-product oil obtained during petroleum refining and petroleum cracking.

So-called petroleum resins belong to this category. Since petroleum-based hydrocarbon resins usually have double bonds in their molecules, they can be carboxylated by reacting with an unsaturated acid such as maleic anhydride.

The carboxylated petroleum hydrocarbon resin can be made into a water-soluble salt using a basic substance such as ammonia, an organic amine, or a caustic alkali.

It is already known that water-soluble salts of carboxylated petroleum-based hydrocarbon resins can be used for surface sizing of paper (Japanese Patent Publication No. 1330/1983).

However, when this is used as a surface coating agent or waterproofing agent for paper, its adhesion to paper is poor and it is difficult to obtain glossy and beautiful waterproofed paper.

Moreover, the water resistance obtained is not necessarily sufficient.

On the other hand, various polyvinyl emulsions such as polystyrene emulsions have been used as coating compositions for a long time, but emulsion compositions generally have major problems in their stability.

That is, when the surface of paper is processed using a high-speed processing device, troubles such as gum up and blocking tend to occur.

When alcohol is added for the purpose of accelerating drying and improving fluidity, aggregates tend to form.

Furthermore, it is difficult to store in the winter because it has no stability against freezing and thawing.

Moreover, the water resistance of the dried coating is not completely satisfactory.

As a result of research to improve the above-mentioned drawbacks, the present inventors have found that an emulsion composition having the structure described in the claims has excellent stability and is stable against high-speed stirring, addition of alcohol, and even freezing and thawing. Moreover, despite being emulsified and dispersed in an aqueous medium, we succeeded in obtaining an emulsion composition that exhibits properties close to those of an aqueous solution.

As the petroleum hydrocarbon resin of the present invention, commercially available petroleum resins and similar products thereof can be used, but from the viewpoint of easy carboxylation of the resin, those with a high bromine value are preferable, and the emulsion composition From the viewpoint of preventing knocking when used, it is desirable that the resin has a high texture.

Therefore, if necessary, two or more types can be mixed in an appropriate ratio to adjust the properties.

Desirable unsaturated acids for use in carboxylating petroleum-based hydrocarbon resins include maleic anhydride, maleic acid, fumaric acid, and itaconic acid.

The amount of the unsaturated acid used must be such that the salt of the basic substance becomes water-soluble, and is usually 8 to 25 weight percent based on the petroleum hydrocarbon resin.

In addition, from the viewpoint of the use of the emulsion composition of the present invention, the basic substance used to make the carboxylated petroleum-based hydrocarbon resin water-soluble is preferably one that decomposes and evaporates during heating and drying. Organic amines are preferable.

The amount of acrylic acid and/or methacrylic acid glycidyl ester reacted with the water-soluble salt of the carboxylated petroleum hydrocarbon resin is suitably about 5 to 30% of the aging equivalent of the resin.

A modified carboxylated petroleum hydrocarbon resin having an unsaturated group (hereinafter simply referred to as a reactant) is obtained by the above reaction.

In the present invention, after emulsifying and dispersing the above-mentioned reactant in an aqueous medium,
A vinyl monomer is dispersed in this and emulsion polymerized to obtain an emulsion composition.

In this case, there is no need to use other emulsifiers or protective colloids, and the use of these may actually reduce the water-resistant effect of the emulsion composition of the present invention.

The weight ratio of the reaction product of the above-mentioned carboxylated petroleum hydrocarbon resin and acrylic acid and/or methacrylic acid glycidyl ester to the vinyl monomer is approximately 2:
The ratio should be about 8 or 8:2.

Emulsion polymerization in this case is usually carried out by adding a radical polymerization initiator, and conventional radical emulsion polymerization techniques can be employed as is.

The vinyl monomer used in the present invention preferably has excellent graft polymerizability and is hydrophobic.

Such vinyl monomers include styrene or its analogs or esters of acrylic acid or methacrylic acid.

In particular, styrene is economically advantageous and has excellent graft polymerizability.

The resulting polymer is hard and has excellent hydrophobicity, and the resulting emulsion is ultrafine and extremely stable, so it is sufficiently stable against mechanical shock, alcohol addition, and freezing and thawing. Film properties can also be improved compared to known ones.

What is more noteworthy is that if styrene is mixed with 2-ethylhexyl acrylate as a vinyl monomer,
It has the remarkable effect of dramatically improving its film-forming properties without reducing its hydrophobicity in any way.

In this case, the ratio of styrene to 2-ethylhexyl acrylate used is in the range of 5:5 to 9:1 by weight.

The details of why the emulsion composition of the present invention exhibits the above-mentioned various effects will require further research in the future, but the combination of the water-soluble salt of carboxylated petroleum resin and the glycidyl acrylic acid and/or methacrylic acid The properties of the polymer obtained by graft polymerization of the reaction product with the ester and the vinyl monomer, and the polymer obtained by emulsion polymerization of both in an aqueous medium, become ultrafine particles, resulting in an emulsion. It is thought that the effects of both are synergistic in that they exhibit properties intermediate between those of aqueous solution and aqueous solution.

As described above, the emulsion composition of the present invention has extremely high emulsion stability, and is resistant to mechanical shock, alcohol addition, etc.
It is also stable against freezing and thawing, so there are no problems such as gum up or knocking during high-speed surface processing of paper.

Furthermore, when the emulsion composition of the present invention is used as a coating composition for paper, it is possible to obtain a paper coating composition that has good adhesion, provides a beautiful glossy processed surface, and has sufficiently satisfactory water resistance.

The emulsion composition of the present invention also includes a paper waterproofing agent,
It can be used for various purposes such as a surface sizing agent for paper, a binder for paints or printing inks, etc.

Next, various production examples of the emulsion composition of the present invention will be shown, as well as test results of various effects when applied to kraft paper and high-quality paper.

For comparison, the test results of an aqueous dispersion of only a water-soluble salt of a carboxylated petroleum resin and an emulsion polymerization of a mixture of styrene and 2-ethylhexyl acrylate are also shown.

[Production Example 1] In a 21-volume four-bottle flask equipped with a stirrer, a thermometer, and a nitrogen inlet, 600 g of petroleum resin (manufactured by Toho Oil Resin Co., Ltd., Toho Hi-Resin #60) and petroleum resin (manufactured by Nippon Oil Co., Ltd., Neo 400 g of polymer≠160) was charged, heated in an oil bath, and at an internal temperature of 165°C, 150 g of maleic anhydride was added, further heated and reacted at an internal temperature of 200 to 225°C for about 8 hours.

The resulting resin had an acid value of 72 and a softening point of 125°C.

Next, 600 g of the above resin, 1280 g of ion-exchanged water, 70 g of jetanolamine, and aqueous ammonia (NH40H28
%) to prepare an aqueous dispersion (hereinafter, this aqueous dispersion will be referred to as aqueous dispersion A).

). 3 g of glycidyl methacrylate was added to the above aqueous dispersion A401 and reacted at 50 to 60°C for 1 hour.
) and thoroughly dispersed.

Next, while blowing nitrogen gas, 2 g of benzoyl peroxide is added at 50 to 60°C to start the polymerization reaction.

The polymerization reaction is completed in about 4 hours. The obtained aqueous dispersion was
Non-volatile content 40%, pH 9.1, viscosity 24cps (25℃
)Met.

[Production Example 2] Production Example 1 except that 280 g of styrene was used instead of MMA used as the vinyl monomer.

The treatment was carried out in exactly the same manner as in Production Example 1 to obtain an aqueous dispersion.

The resulting aqueous dispersion had a nonvolatile content of 40%, a pH of 9.1, and a viscosity of 18 cps.

[Production Example 3] Instead of MMA used as the vinyl monomer in Production Example 1, 168 g of styrene and 112 g of 2-ethylhexyl acrylate (styrene: 2-ethylhexyl acrylate = 6:4 weight ratio) were used. was treated in exactly the same manner as in Production Example 1 to obtain an aqueous dispersion.

The resulting aqueous dispersion had a nonvolatile content of 40%. The pH was 9.0 and the viscosity was 20 cps (25°C).

[Production Example 4] The weight ratio of styrene and 2-ethylhexyl acrylate in Production Example 3 was set to 7=3, and otherwise the process was carried out in exactly the same manner as in Production Example 3 to obtain an aqueous dispersion.

The resulting aqueous dispersion had a nonvolatile content of 40%, a pH of 9.0, and a viscosity of 19 cps.

[Production Example 5] The weight ratio of styrene and 2-ethylhexyl acrylate in Production Example 3 was set to 8=2, and otherwise the process was carried out in exactly the same manner as in Production Example 3 to obtain an aqueous dispersion.

The resulting aqueous dispersion had a non-volatile content of 40% and p! (9,0,
The viscosity was 18 cps.

[Production Example 6] Toho Hi-Resin 4P60100 was prepared in the same manner as in Production Example 1.
0 g, and 200 g of maleic anhydride was reacted therewith.

The obtained resin had an acid value of 92 and a softening point of 110°C.

Next, the above resin 600I was mixed with dimethylethanolamine 6
An aqueous dispersion was prepared using 0g of ammonia, 42g of ammonia water (NH, 0H2S%), and 1298y of ion-exchanged water (hereinafter referred to as aqueous dispersion B).

Aqueous dispersion B4O0g, glycidyl methacrylate 3g, ion exchange water 320g, styrene 196g, acrylic acid 2
- Ethylhexyl sog (styrene: 2-ethylhexyl acrylate = 7 = 3 weight ratio), benzoyl peroxide 2g
An aqueous dispersion was obtained.

The resulting aqueous dispersion had a nonvolatile content of 40%, a pH of 8.0, and a viscosity of 21 cps.

[Production Example 7] An aqueous dispersion was obtained in the same manner as in Production Example 6 except that the weight ratio of styrene and 2-ethylhexyl acrylate was changed to 8=2.

The resulting aqueous dispersion had a nonvolatile content of 40.2% and a pH of 8.1.
, and the viscosity was 19 cps.

[Production Example 8] An aqueous dispersion was obtained in the same manner as in Production Example 6 except that 2.5 g of glycidyl acrylate was used instead of 3 g of glycidyl methacrylate in Production Example 6.

The resulting aqueous dispersion had a nonvolatile content of 40%, a pH of 9.0, and a viscosity of 21 cps.

[Reference example 1] Aqueous dispersion A in Production Example 1 was used.

[Reference Example 2] By normal emulsion polymerization method, 2 g of nonionic activator Emuljit B-25 (manufactured by Dai-Kogyo Yakuhin Co., Ltd.) and 2 g of nonionic activator Emuljit B-25 (manufactured by Dai-Kogyo Yakuhin Co., Ltd.) and 597 g of ion-exchanged water and monogen Y-100 (manufactured by Dai-Kogyo Yakuhin Co., Ltd.), an anion activator were added to 597 g of ion-exchanged water.
(manufactured by Kogyo Yakuhin Co., Ltd.) 1 was added and thoroughly dispersed, and to this was added 240 g of styrene and 16 g of 2-ethylhexyl acrylate.
0g was emulsion polymerized.

The resulting aqueous dispersion had a nonvolatile content of 4040.5% and a pH of 8.
,0, and the viscosity was 50 cps.

Reference Example 3 In Production Example 1, the same procedure as in Production Example 1 was carried out except that glycidyl methacrylate was not reacted.

The resulting aqueous dispersion had a nonvolatile content of 40%, a pH of 9.3, and a viscosity of 20 cps.

Reference example 4 Petroleum resin (Toho) 1 Iresin #60 used in production example 1
) 120.9 to 280 g of methyl methacrylate (MMA)
dissolved in.

The obtained MMA solution of petroleum resin was mixed with 2 g of nonionic activator emulsion) E-25° and anionic activator Monogen Y.
-100, Ig-containing ion-exchanged water 59 (Bi') was added and sufficiently stirred and dispersed, and 10 g of a 6% ammonium persulfate aqueous solution was added for emulsion polymerization.

The obtained aqueous dispersion partially liberates petroleum resin and is filtered and removed.
Its nonvolatile content is 34.4%, pH is 6.5, and viscosity is 21c.
It was ps.

[Test Example 1] The products obtained in Production Examples 1 to 8 and Reference Examples 1 and 2 described above were coated on kraft paper with bar coater No. 8, and various properties were tested. The results are as shown in Table 1. there were.

(Note) 1 ◎ Excellent, ○ Good, △ Fair, × Poor 2 Test method (1) Gloss: Visual judgment (2) Blocking resistance: Temperature 40°C, humidity 90%, load 100 g/cd 24 hours (3) Water resistance: Place a water droplet on the test piece, remove the water droplet with P paper after 5 minutes, and observe the state of the coating film.

(4) Water repellency: Place a drop of water on the test piece and observe the state at that time.

(5) Alcohol stability: Add 5 g of isopropyl alcohol to 100 g of the aqueous dispersion and observe changes in the emulsion.

(6) Freezing stability: Store the aqueous dispersion at -10°C, freeze, and then return to room temperature.

Repeat this three times and observe the changes. [Test example 2
] The emulsion composition obtained in Production Example 3 was diluted with water to give a non-volatile content of 0.1%, and coated on high-quality paper (65 g/m2 Steckigt size) using a test roll coater (double-sided coating 3 m/sec). 12 seconds) surface sizing was performed.

The Steckigt sizing degree of the obtained paper was 31.1 seconds.

At this time, the resin content absorbed into the paper by surface sizing was equivalent to 0.018% of the paper.

Surface sizing was performed in exactly the same manner using a commercially available surface sizing agent (trade name Coropal M-305, manufactured by Seiko Kagaku Kogyo Co., Ltd.).

The Steckigt sizing degree of the obtained paper was 30.1 seconds.

(Absorbed resin content is 0.019% of paper)

Claims (1)

[Claims] 1. A water-soluble salt of a carboxylated petroleum-based hydrocarbon resin;
A vinyl heavy substance is dispersed in an aqueous medium containing a modified carboxylated petroleum-based hydrocarbon resin having an unsaturated group, which is a reaction product of acrylic acid and/or methacrylic acid glycidyl ester, and emulsion polymerization is carried out. An emulsion composition containing a petroleum-based hydrocarbon resin. 2. The petroleum hydrocarbon resin-containing emulsion composition according to claim 1, wherein the vinyl heavy substance is a mixture of styrene and 2-ethylhexyl acrylate.