JP2001261815A - Alkylene oxide adduct of aromatic hydrocarbon formaldehyde resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkylene oxide adduct of aromatic hydrocarbon formaldehyde resin having excellent emulsifiability and imparting pressure-sensitive adhesiveness and adhesiveness to an aqueous acrylic resin, urethane resin, or epoxy resin. SOLUTION: An alkylene oxide is added to an aromatic hydrocarbon/ formaldehyde resin and a modified aromatic hydrocarbon/formaldehyde resin to form the adduct.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic hydrocarbon formaldehyde resin and a modified aromatic hydrocarbon formaldehyde resin having excellent emulsification stability, corrosion resistance and water resistance and having a self-emulsifying function and a surface active function. , Adhesives, adhesives, sizing agents and the like.

[0002]

2. Description of the Related Art Aromatic hydrocarbon formaldehyde resins are used as non-reactive modifiers and reactive modifiers, such as acrylic resin, urethane resin, epoxy resin, etc., for the water resistance, corrosion resistance, adhesion and the like. Widely used to improve properties. 2. Description of the Related Art In recent years, restrictions on the use of solvents have been becoming stricter due to the danger of fire due to the use of solvents, pollution problems associated with air pollution, and the effects on human bodies. In order to eliminate this adverse effect, development of an aromatic hydrocarbon formaldehyde resin that can be used in an aqueous system has been desired.

As an aromatic hydrocarbon formaldehyde resin that can be used in an aqueous system, for example, Nikanol GEM100, which is produced by high-speed stirring with a homomixer using a surfactant, is used.
Nikanol GEM200 (trade name of Mitsubishi Gas Chemical Co., Ltd.) is known.

[0004]

Problems to be Solved by the Invention Nicananol GEM100 and Nicanol GEM200 are demanded to have further improved water resistance and adhesion. Addition of an external surfactant is considered to impair water resistance and adhesion, and a method of emulsifying a modified aromatic hydrocarbon formaldehyde resin without using a surfactant is desired.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that by adding an alkylene oxide to an aromatic hydrocarbon formaldehyde resin and a modified aromatic hydrocarbon formaldehyde resin, an excellent self-adhesion is achieved. The inventors have found that they have an emulsifying function or a surface active function, and have completed the present invention.

That is, the present invention provides an aromatic hydrocarbon formaldehyde resin and an aromatic hydrocarbon formaldehyde resin modified with phenols and polyols, wherein an alkylene oxide is added to active hydrogen under an alkali catalyst. The present invention relates to the synthesis of a polyalkylene oxide block copolymer of a modified aromatic hydrocarbon formaldehyde resin.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A self-emulsifying property can be obtained by block copolymerizing an aromatic hydrocarbon formaldehyde resin and a modified aromatic hydrocarbon formaldehyde resin with 10 phr or more, preferably 15 phr or more of alkylene oxide. . 10 phr of alkylene oxide
When the amount is less, it is not preferable because it does not have a satisfactory self-emulsifying function.

A useful surfactant having a surface active function can be obtained by block copolymerizing an aromatic hydrocarbon formaldehyde resin and a modified aromatic hydrocarbon formaldehyde resin with 500 phr or more of an alkylene oxide.

The aromatic hydrocarbon used as a raw material of the aromatic hydrocarbon formaldehyde resin used in the present invention includes three isomers of toluene and xylene, mesitylene, pseudocumene, and monocyclic aromatic hydrocarbons having 10 or more carbon atoms. And polycyclic aromatic hydrocarbon compounds such as naphthalene and methylnaphthalene. In addition, these mixtures can also be used.

Examples of the formaldehyde include industrially easily available compounds that generate formaldehyde, such as formalin, paraformaldehyde, and trioxane.

The phenol-modified aromatic hydrocarbon formaldehyde resin is obtained by reacting the aromatic hydrocarbon formaldehyde resin with phenol with an acid catalyst. As the phenol, phenol, cresol, butyl phenol, nonyl phenol or the like is used. Can be.

The polyol-modified aromatic hydrocarbon formaldehyde resin is obtained by reacting an aromatic hydrocarbon formaldehyde resin and a polyol with an acid catalyst. Examples of the polyol include ethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol. , Trimethylolpropane, neopentyl glycol and the like can be used.

As the alkylene oxide, ethylene oxide, propylene oxide and a mixture thereof can be used.

In this reaction, caustic soda, caustic potash, sodium methoxide, potassium methoxide, triethylamine and the like can be used as a catalyst.

In this case, the reaction temperature is usually 100 to 190 ° C., preferably 140 to 170 ° C., and the reaction time is 3 to 30 hours, preferably 5 to 15 hours.

In the present invention, an aromatic hydrocarbon formaldehyde resin having a self-emulsifying function is obtained by block copolymerizing an aromatic hydrocarbon formaldehyde resin and a modified aromatic hydrocarbon formaldehyde resin with 10 phr or more, preferably 15 phr or more of ethylene oxide. And a modified aromatic hydrocarbon formaldehyde resin, which can be used as a water-based acrylic resin adhesive, a paint, a water-based urethane resin adhesive, a paint, a water-based epoxy resin adhesive, a paint, and the like. In addition, it can be used with conventional additives such as reactive diluents, non-reactive diluents, fillers, pigments and plasticizers. Further, it can be used together with a thixotropic agent, a flame-retardant substance and the like.

A block copolymer of an aromatic hydrocarbon formaldehyde resin and a modified aromatic hydrocarbon formaldehyde resin with 500 phr or more of ethylene oxide has a surface active function and emulsifies an epoxy resin, a urethane resin and an acrylic resin. I can do things.

The alkylene oxide adduct of the aromatic hydrocarbon formaldehyde resin having a self-emulsifying function of the present invention has excellent emulsifiability, and is a water-based acrylic resin adhesive.
Water resistance, corrosion resistance, by using for paint, water-based urethane resin adhesive, paint, water-based epoxy resin adhesive, paint, etc.
Demonstrates excellent effect on adhesion. An alkylene oxide adduct of an aromatic hydrocarbon formaldehyde resin having a surface active function can emulsify an acrylic resin, a urethane resin, an epoxy resin, etc., and gives a stable emulsion.

[0019]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples.

Nicanol L (100% xylene resin manufactured by Mitsubishi Gas Chemical Co., Ltd.) Hydroxyl equivalent 1600 (g / eq) Nicanol K100 (Trimethylopropane-modified xylene resin manufactured by Mitsubishi Gas Chemical Co., Ltd.) Hydroxyl equivalent 660 (g / eq) Nicanol K140 (Trimethylopropane-modified xylene resin manufactured by Mitsubishi Gas Chemical Co., Ltd.) Hydroxyl equivalent 200 (g / eq) Nicanol HP70 (tert-butylphenol-modified xylene resin manufactured by Mitsubishi Gas Chemical Co., Ltd.) Hydroxyl equivalent 600 (g / eq.) eq)

[Production Example 1] In a stainless steel autoclave equipped with a thermometer, a stirrer, a nitrogen inlet tube, a cooling tube, and an alkylene oxide inlet tube, 100 g of Nicanol L and 0.1 g of potassium hydroxide were charged, and 33 g of ethylene oxide was reacted. The reaction was carried out by feeding at a temperature of 160 to 170 ° C. and a pressure of 2 atm for 4 hours to obtain a self-emulsifying resin (A) having a hydroxyl equivalent of 1720 (g / eq).

[Production Example 2]
100 g of K100 and 0.1 g of potassium hydroxide were charged, and 33 g of ethylene oxide was added at a reaction temperature of 160 to 170 ° C. under a pressure of 2 atm.
The reaction was carried out by feeding for a time to obtain a self-emulsifying resin (B) having a hydroxyl equivalent of 860 (g / eq).

[Production Example 3]
100 g of K140 and 0.1 g of potassium hydroxide were charged and 33 g of ethylene oxide was added at a reaction temperature of 160 to 170 ° C. under a pressure of 2 atm.
The reaction was carried out by feeding for a time to obtain a self-emulsifiable resin (C) having a hydroxyl equivalent of 270 (g / eq).

[Production Example 4]
100 g of HP70 and 0.1 g of potassium hydroxide were charged, and 33 g of ethylene oxide was added at a reaction temperature of 160 to 170 ° C. under a pressure of 2 atm.
The reaction was carried out by feeding for a time to obtain a self-emulsifiable resin (D) having a hydroxyl group equivalent of 730 (g / eq).

[Production Example 5] As in Production Example 1, 100 g of Nicanol L and 0.1 g of potassium hydroxide were charged, and 100 g of ethylene oxide was added at a reaction temperature of 160 to 170 ° C. under a pressure of 2 atm.
The reaction was carried out by feeding for a time to obtain a self-emulsifiable resin (E) having a hydroxyl equivalent of 2500 (g / eq).

[Production Example 6]
100 g of K100 and 0.1 g of potassium hydroxide were charged and 200 g of ethylene oxide was added at a reaction temperature of 160 to 170 ° C. under a pressure of 2 atm.
The reaction was carried out by feeding for a time to obtain a self-emulsifiable resin (F) having a hydroxyl equivalent of 1940 (g / eq).

[Production Example 7]
100 g of K140 and 0.1 g of potassium hydroxide were charged, and 300 g of ethylene oxide was added at a reaction temperature of 160 to 170 ° C. under a pressure of 2 atm.
The reaction was carried out by feeding for a time to obtain a self-emulsifiable resin (G) having a hydroxyl equivalent of 810 (g / eq).

[Production Example 8] In the same manner as in Production Example 1, 100 g of Nicanol L and 0.1 g of potassium hydroxide were charged, and 900 g of ethylene oxide was added at a reaction temperature of 160 to 170 ° C. under a pressure of 2 atm.
The reaction was carried out by feeding for a time to obtain a self-emulsifiable resin (H) having a hydroxyl equivalent of 5800 (g / eq).

[Comparative Production Example 1] In the same manner as in Production Example 1, Nicanol L (100 g) and potassium hydroxide (0.1 g) were charged, and ethylene oxide (5 g) was fed at a reaction temperature of 160 to 170 ° C. and a pressure of 2 atm for 4 hours to carry out a reaction. Resin (I) having a hydroxyl equivalent of 1270 (g / eq) was obtained. This resin did not show self-emulsifiability.

"Preparation of acrylic emulsion (I)" n-
48 parts by weight of butyl acrylate, 48 parts by weight of 2-ethylhexyl acrylate, 4 parts by weight of acrylic acid, ammonium salt of polyoxyethylene nonylphenyl ether sulfate with a propenyl group ("Aklon HS-10" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.6
A mixture consisting of parts by weight and 0.05 parts by weight of dodecyl mercaptan was emulsified using 30 parts by weight of ion-exchanged water to obtain an emulsified monomer. Next, 70 parts by weight of ion-exchanged water and 0.1 part by weight of potassium persulfate were charged into the reactor, and polymerization was carried out over 4 hours in a nitrogen atmosphere at 80 ° C. while dropping the emulsified monomer. After completion of the dropwise addition, polymerization was further carried out at 80 ° C. for 3 hours to obtain an acrylic emulsion (I) (solid content: 50%).
% By weight).

[Example 1] Acrylic emulsion (I)
15 parts by weight of the resin (A) was added to 200 parts by weight and stirred to obtain an acrylic emulsion composition.

Example 2 Acrylic Emulsion (I)
To 200 parts by weight, 15 parts by weight of the resin (B) were added and stirred to obtain an acrylic emulsion composition.

Example 3 Acrylic Emulsion (I)
To 200 parts by weight, 15 parts by weight of the resin (C) were added and stirred to obtain an acrylic emulsion composition.

Example 4 Acrylic Emulsion (I)
To 200 parts by weight, 15 parts by weight of the resin (D) were added and stirred to obtain an acrylic emulsion composition.

Example 5 Acrylic emulsion (I)
15 parts by weight of the resin (E) was added to 200 parts by weight and stirred to obtain an acrylic emulsion composition.

Example 6 Acrylic Emulsion (I)
15 parts by weight of the resin (F) was added to 200 parts by weight and stirred to obtain an acrylic emulsion composition.

Example 7 Acrylic Emulsion (I)
15 parts by weight of the resin (G) was added to 200 parts by weight and stirred to obtain an acrylic emulsion composition.

Comparative Example 1 Acrylic Emulsion (I)
To 200 parts by weight, 30 parts by weight of tackifier emulsion ("Superester E740" manufactured by Arakawa Chemical Co., Inc., component: uneven rosin ester) was added and stirred to obtain an acrylic emulsion composition.

The acrylic emulsion compositions obtained in the above Examples and Comparative Examples were evaluated for mechanical stability (coating stability) by the following method, and the results are shown in Table 1. (Measurement method of mechanical stability) Using a Marlon-type mechanical stability tester (Kyowa Interface Chemical Co., Ltd., emulsion / latex mechanical stability characteristic measurement-recorder [CMS-A type]), 50 g of acrylic resin After rotating the emulsion composition under a pressure of 10 kg / cm ² at a rotation speed of 1000 rpm for 5 minutes, the aggregate in the container was filtered through a 100-mesh wire gauze, and dried at 110 ° C. for 3 hours. The ratio of the dry weight to the total solid content was calculated by the following formula, and used as an index of stability. Mechanical stability (% by weight) = ｛Aggregate dry weight (g) / [50 (g) ×
Solid content (% by weight)]｝ × 100

The above-mentioned solid content concentration was calculated by the following formula after 1.5 g of the acrylic emulsion composition was placed in an aluminum cup, dried at 110 ° C. for 3 hours, and the dry weight of the acrylic emulsion composition was measured. did. Solid content concentration (% by weight) = [dry weight (g) /1.5 (g)] × 100

[0041]

[Table 1] Even if an alkylene oxide adduct of an aromatic hydrocarbon formaldehyde resin having a self-emulsifying function and an alkylene oxide adduct of a modified aromatic hydrocarbon formaldehyde resin having a self-emulsifying function are added to the acrylic emulsion (I), Has excellent mechanical stability. Therefore, it can be used as a pressure-sensitive adhesive in applications where a high shear force is applied.

"Preparation of urethane emulsion (II)" Polypropylene glycol diol having a number average molecular weight of 10,000 (trade name "Preminol 4010" manufactured by Asahi Glass Co., Ltd., OH value 11)
50 parts by weight, 50 parts by weight of polypropylene glycol diol having a number average molecular weight of 2000 (trade name: Nissan Uniol D-2000, OH value 58, manufactured by NOF Corporation), 3-isocyanatomethyl-3,5-5-trimethylcyclohexyl isocyanate (Hurth, trade name "Bestant IPDI") 32.2
Parts by weight, 5.6 parts by weight of dimethylolpropionic acid (trade name "DMPA", manufactured by Trimet Technical Products Co., Ltd.)
[Equivalent ratio of [isocyanate group / hydroxyl group] = 2.0) and a mixed solution consisting of 34.5 parts by weight of methyl ethyl ketone was subjected to boiling point polymerization with stirring to reduce the isocyanate group content to 3.5% by weight or less and to adjust the viscosity. 57.4 parts by weight of methyl ethyl ketone and triethylamine as a neutralizing agent 4.
2 parts by weight were added. Next, 250 parts by weight of water was added while vigorously stirring the reaction mixture at room temperature, and immediately thereafter, 20 parts by weight of a 20% by weight aqueous solution of ethylenediamine (solid content:
4.0 parts by weight) and further stirred at room temperature for 1 hour, and then the pressure was reduced and the solvent was removed to obtain a urethane emulsion (II) having a solid content of 40%.

Example 8 Urethane emulsion (II)
10 parts by weight of the resin (A) was added to 200 parts by weight and stirred to obtain a urethane emulsion composition.

Example 9 Urethane emulsion (II)
10 parts by weight of the resin (B) was added to 200 parts by weight and stirred to obtain a urethane emulsion composition.

Example 10 Urethane emulsion (I
I) 10 parts by weight of resin (C) was added to 200 parts by weight and stirred to obtain a urethane emulsion composition.

Example 11 Urethane emulsion (I
I) 10 parts by weight of the resin (D) was added to 200 parts by weight and stirred to obtain a urethane emulsion composition.

Example 12 Urethane emulsion (I
I) 10 parts by weight of the resin (E) was added to 200 parts by weight and stirred to obtain a urethane emulsion composition.

Example 13 A urethane emulsion (I
I) 10 parts by weight of resin (F) was added to 200 parts by weight and stirred to obtain a urethane emulsion composition.

Example 14 Urethane emulsion (I
I) 10 parts by weight of the resin (G) was added to 200 parts by weight and stirred to obtain a urethane emulsion composition.

(Evaluation) The urethane-based aqueous compositions obtained in Examples 8 to 14 were evaluated for normal adhesion to cold-rolled steel sheets and normal adhesion to flexible boards by the following methods.

[Normal adhesion to cold-rolled steel sheet] The obtained aqueous composition was coated with a hood cloth and a cold-rolled steel sheet (width 25 mm, length 125 mm,
The thickness is 2 mm), and the amount of coating and the solid content are 100 (g / cm ² ) on the canvas and 40 (g / cm ² ) on the cold-rolled steel sheet.
cm ² ) and dried in an air drying oven at 80 ° C. for 4 minutes, and then roll-pressed at a pressure of 60 kg / 25 mm to prepare a test piece. After curing the test piece at 23 ° C for 1 week,
At 90 ° C., a 90 ° peel test was performed at a pulling speed of 50 mm / min.

[Adhesion to flexible board in normal state] The obtained aqueous composition was applied to a canvas and a flexible board (25 m wide).
m, length 125 mm, thickness 2.5 mm) by brush application, applied on canvas at a coating amount and solid content of 100 (g / cm ² ), and applied on a flexible board at 60 (g / cm ² ). After drying in a blow drying oven for 4 minutes, pressure 60Kg / 25m
Both were roll-pressed at m to prepare a test piece. The test piece was cured at 23 ° C. for one week, and then subjected to a 90 ° peel test at 23 ° C. at a pulling speed of 50 mm / min. Table 2 shows the evaluation results.

[0053]

[Table 2] By adding the aromatic hydrocarbon formaldehyde resin having a self-emulsifying function and the modified aromatic hydrocarbon formaldehyde resin of the present invention to the urethane emulsion (II), excellent adhesion to metals and porous materials in a normal state is provided. You can do it.

“Preparation of Epoxy Resin Emulsion”

Example 15 1 equipped with an squid-type stirrer
200 g of Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.) was charged into an L flat-bottom separable flask, and 10 g of resin (H) was dispersed and added to 20 g of water, followed by stirring at room temperature for 30 minutes at a stirring speed of 100 rpm. Thereafter, 180 g of water was gradually added, and an epoxy resin emulsion having a solid content of 50% was obtained by a phase inversion method.

Example 16 1 equipped with an squid-type stirrer
200 g of Epicoat 1001 × 75 (manufactured by Yuka Shell Epoxy Co., Ltd.) was charged into an L flat bottom separable flask, and 10 g of resin (H) was dispersed and added to 20 g of water, followed by stirring at room temperature for 30 minutes at a stirring speed of 100 rpm. . Thereafter, 180 g of water was gradually added, and an epoxy resin emulsion having a solid content of 50% was obtained by a phase inversion method.

Comparative Example 2 Neugen EA was used instead of 10 g of the resin (H) of Example 15.
An epoxy resin emulsion having a solid content of 50% was obtained by using 10 g of 160. Neugen EA160: Nonylphenol EO adduct H
LB16 (Daiichi Kogyo Seiyaku Co., Ltd.)

The emulsifying properties of the resins obtained in Examples 15 and 16 were evaluated, and then cured with Adeka Hardener EH-220 (Asahi Denka Kogyo Co., Ltd., active hydrogen equivalent = 76, modified aliphatic amine). The coating film properties were evaluated. The method for preparing the coating film and the evaluation method are described below.

[Emulsifying property] When the emulsification was good,
The case where separation occurs is indicated by △, and the case where emulsification is not performed × Method for preparing coating film Coated plate: Cold rolled steel sheet (JIS G3141, SPCC-SB, 150X70
X0.8mm) treated with sundink (# 240) and used after washing xylene Coating: Use 200μ doctor blade Curing condition: 7 days / 23 ℃, 50% RH Coating condition When the coating film is formed well and is glossy 、, × when film formation was not possible. Adhesiveness A peeling test was performed with a tape in a 100 cross-cut square. O: No change when immersed in water for 7 days, B: Blister, swelling, whitening occurred. Corrosion resistance ○: No change when immersed in 5% saline for 7 days, ×: Blister, blistering, whitening. Alkali resistance: No change when immersed in a 10% aqueous sodium hydroxide solution for 7 days, and x: when blistering, blistering, and whitening occurred. Hardness The hardness of the coating film was evaluated based on pencil hardness. The evaluation results are shown in Table-3

[0060]

[Table 3] The epoxy resin obtained by emulsifying the aromatic hydrocarbon formaldehyde resin having a self-emulsifying function of the present invention as an emulsifier has excellent emulsifying properties, and a coating film having excellent adhesiveness, water resistance, corrosion resistance, and alkali resistance can be obtained. Can be done.

[0061]

According to the present invention, an alkylene oxide adduct of an aromatic hydrocarbon formaldehyde resin having a self-emulsifying function and an alkylene oxide of a modified aromatic hydrocarbon formaldehyde resin having a self-emulsifying function in order to improve the adhesive properties of the acrylic emulsion (I). Excellent mechanical stability is maintained even when an additive is added. Therefore, it can be used as an adhesive in applications where a high shear force is applied. The addition of the alkylene oxide adduct of an aromatic hydrocarbon formaldehyde resin and the alkylene oxide adduct of a modified aromatic hydrocarbon formaldehyde resin having a self-emulsifying function of the present invention to a urethane emulsion (II) allows the formation of a metal and a porous material in a normal state. Excellent adhesion to materials can be provided. The epoxy resin obtained by emulsifying the alkylene oxide adduct of the aromatic hydrocarbon formaldehyde resin having a surface active function of the present invention as an emulsifier has excellent emulsifying properties, and has excellent adhesiveness, water resistance, corrosion resistance, and alkali resistance. A coating film can be obtained.

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Claims (6)

[Claims] 1. An aromatic hydrocarbon formaldehyde resin and a modified aromatic hydrocarbon formaldehyde resin obtained by adding an alkylene oxide to an aromatic hydrocarbon formaldehyde resin and a modified aromatic hydrocarbon formaldehyde resin. 2. The aromatic hydrocarbon is toluene, xylene,
The aromatic hydrocarbon formaldehyde resin according to claim 1, which is mesitylene or pseudocumene. 3. The modified aromatic hydrocarbon formaldehyde resin according to claim 1, wherein the modified aromatic hydrocarbon formaldehyde resin is obtained by modifying an aromatic hydrocarbon formaldehyde resin with phenols or polyols. 4. The phenol is any one of phenol, cresol, butylphenol and nonylphenol.
4. The phenol-modified aromatic hydrocarbon formaldehyde resin of claim 3 which is at least one species. 5. The polyol-modified aromatic hydrocarbon formaldehyde resin according to claim 3, wherein the polyol is at least one of ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, trimethylolpropane, and neopentyl glycol. 6. The aromatic hydrocarbon formaldehyde resin and the modified aromatic hydrocarbon formaldehyde resin according to claim 1, wherein the alkylene oxide is ethylene oxide.