TW202130735A - Carbamate resin composition and method for producing porous body capable of producing a porous body with excellent wet film forming properties and low compressibility - Google Patents

Abstract

The problem to be solved by the present invention is to provide a method for producing a porous body having excellent wet film-forming properties and low compressibility. The present invention provides a urethane resin composition, which contains a urethane resin (A), a solvent (B) and a film-forming aid (C), characterized in that the film-forming aid (C) Contains hydrocarbons (c1) in the range of 8 to 18 carbon atoms. In addition, the present invention provides a method for producing a porous body, characterized in that the urethane resin composition is subjected to wet film formation. The content of the hydrocarbon (c1) is preferably in the range of 0.1 parts by mass to 30 parts by mass relative to 100 parts by mass of the urethane resin (A). The hydrocarbon (c1) is preferably an isoparaffin.

Description

Urethane resin composition and method for producing porous body

The present invention relates to a urethane resin composition and a method for manufacturing a porous body based on a wet film forming method.

In fields requiring high surface flatness, such as liquid crystal glass, hard disk glass, silicon wafers, and semiconductors, polishing pads using urethane resin compositions are widely used. Among them, in the final finishing polishing, a soft porous body is used. The soft porous body is made of urethane resin diluted with a solvent such as dimethyl formamide (DMF). It is processed by a wet film-forming method that solidifies in water (for example, refer to Patent Document 1).

The characteristics required for the polishing pad based on the porous body include, for example, a material having a high bulk elastic modulus (=low compressibility) for maintaining the flatness of the surface of the processed body, and a material that suppresses scratches on the surface Flexibility, fineness and uniformity (wet film forming properties) of the porous unit responsible for the maintenance of the slurry (polishing liquid) and stable polishing.

However, the aforementioned low compressibility, flexibility, and wet film-forming properties are the opposite physical properties. For example, when flatness is emphasized and a low compressibility of the polishing pad is tried, the urethane resin is hardened. , The scratches worsen. In addition, when the scratch property is emphasized and the hardness of the urethane resin is lowered, the coagulation in water does not proceed quickly, thereby losing the uniformity of the porous unit and causing the instability of polishing. As such, it is difficult to balance all physical properties with a high balance. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-256738

[The problem to be solved by the invention] The problem to be solved by the present invention is to provide a method for producing a porous body having excellent wet film-forming properties and low compressibility.

[Technical means to solve the problem] The present invention provides a urethane resin composition, which contains a urethane resin (A), a solvent (B) and a film-forming aid (C), characterized in that the film-forming aid (C) Contains hydrocarbons (c1) in the range of 8 to 18 carbon atoms.

In addition, the present invention provides a method for producing a porous body, characterized in that the urethane resin composition is wet-formed into a film.

[Effects of the invention] According to the present invention, by using a specific film-forming auxiliary agent, a fine and uniform porous body with a low compression rate can be manufactured by a wet film-forming method. Therefore, the present invention can be particularly suitable for the manufacture of polishing pads, artificial leather, and synthetic leather.

In addition, in the present invention, the "porous body" refers to a large number of pores that can be obtained naturally if the urethane resin composition is solidified by a wet film forming method, for example, in a surface In the thickness direction, a long spindle-shaped or teardrop-shaped porous structure is formed.

The present invention is a method for producing a porous body by wet-forming a urethane resin composition containing a urethane resin (A), a solvent (B), and a specific film-forming aid (C).

In the present invention, as the film-forming aid (C), it is necessary to contain a hydrocarbon (c1) having a carbon number in the range of 8-18. The hydrophobicity of the hydrocarbon with the specific carbon number is moderately high. Therefore, by adjusting the solidification rate of the urethane resin in water, the substitution of DMF and water is relaxed, and the surface solidification is suppressed to achieve wet film formation. The miniaturization and uniformity of the porous unit, while obtaining a porous body with low compressibility. As the hydrocarbon, when a hydrocarbon with less than 8 carbon atoms is used, it is ineffective in suppressing the rate of surface solidification, and a porous body with excellent low compressibility cannot be obtained. In addition, when a hydrocarbon with more than 18 carbon atoms is used , The hydrophobicity is too strong, and the uniformity of the porous unit is poor. Furthermore, when a highly hydrophilic film-forming auxiliary agent is used instead of the hydrocarbon (c1), the porous unit becomes enlarged, the wet film-forming property deteriorates, and the compressibility increases. The number of carbon atoms of the hydrocarbon (c1) is preferably in the range of 9-16, and more preferably in the range of 10-14 in terms of achieving a higher level of wet film-forming properties and low compressibility.

The hydrocarbon (c1) has the number of carbon atoms in the specific range and contains only carbon atoms and hydrogen atoms. Examples thereof include normal paraffins, isoparaffins, aromatic compounds, and naphthenic acid compounds. These compounds may be used alone or in combination of two or more kinds. Among these, isoparaffins are preferred in terms of achieving both wet film-forming properties and low compressibility at a higher level.

The density of the hydrocarbon (c1) at 15°C is preferably in the range of 0.7 g/cm ³ to 0.83 g/cm ³ in terms of achieving a higher level of wet film formation and low compressibility. , More preferably in the range of 0.7 g/cm ³ to 0.8 g/cm ³ .

In the film-forming auxiliary agent (C), in addition to the hydrocarbon (c1), other film-forming auxiliary agents may be used in combination. The content of the hydrocarbon (c1) in the film-forming aid (C) is preferably 30% by mass or more in terms of achieving a higher level of wet film-forming properties and low compressibility. More preferably, it is 70% by mass or more.

In addition, as the content of the hydrocarbon (c1), relative to 100 parts by mass of the urethane resin (A), it is preferably in the range of 0.1 part by mass to 30 parts by mass, and more preferably in the range of 1 part by mass to 25 parts by mass. The range of parts by mass.

As the urethane resin (A) used in the present invention, for example, a reaction product of a polyol (a1) and a polyisocyanate (a2) can be used.

As said polyol (a1), polyester polyol, polyether polyol, polycarbonate polyol, etc. can be used, for example. These polyols may be used alone or in combination of two or more kinds.

The number average molecular weight of the polyol (a1) is preferably in the range of 500 to 10,000, and more preferably in the range of 700 to 8,000 in terms of the mechanical properties and flexibility of the porous body. In addition, the number average molecular weight of the polyol (a1) represents a value measured by a gel permeation chromatography (GPC) method.

In the polyol (a1), if necessary, a chain extender (a1-1) having a number average molecular weight of less than 500 may be used in combination. As the chain extender (a1-1), for example, a chain extender having a hydroxyl group, a chain extender having an amine group, and the like can be used. These chain extenders (a1-1) may be used alone or in combination of two or more kinds.

As the chain extender having a hydroxyl group, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol can be used. Alcohol, hexamethylene glycol, sucrose, methylene glycol, glycerin, sorbitol and other aliphatic polyhydric alcohol compounds; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-di Aromatic polyol compounds such as hydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, hydrogenated bisphenol A, and hydroquinone; water, etc. These chain extenders may be used alone or in combination of two or more kinds.

As the chain extender having an amine group, for example, ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2, 5-Dimethylpiperazine, Isophoronediamine, 4,4'-Dicyclohexylmethanediamine, 3,3'-Dimethyl-4,4'-Dicyclohexylmethanediamine, 4, 4'-diphenylmethanediamine, 3,3'-dichloro-4,4'-diphenylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, Aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, etc. These chain extenders may be used alone or in combination of two or more kinds.

As the polyisocyanate (a2), for example, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate can be used , Crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate and other aromatic polyisocyanates; hexamethylene diisocyanate, lysine diisocyanate Aliphatic polyisocyanates such as isocyanates; alicyclic polyisocyanates such as cyclohexane diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, etc. These polyisocyanates may be used individually or in combination of 2 or more types.

As a method for producing the urethane resin (A), for example, adding the polyol (a1), the polyisocyanate (a2), and the chain extender (a1- 1) The method of manufacturing by making it react. These reactions are preferably carried out at a temperature of 50°C to 100°C for approximately 3 hours to 10 hours. In addition, the reaction can also be carried out in the solvent (B) described later.

The molar ratio [ (Hydroxyl group and amino group)/(isocyanate group)], preferably in the range of 0.8 to 1.2, more preferably in the range of 0.9 to 1.1.

As the weight average molecular weight of the urethane resin (A) obtained by the above method, in terms of the mechanical strength and flexibility of the porous body, it is preferably in the range of 5,000 to 1,000,000, more preferably 10,000 to The range of 500,000. In addition, the weight average molecular weight of the said urethane resin (A) shows the value measured similarly to the number average molecular weight of the said polyol (a1).

As content of the said urethane resin (A), the range of 10 mass parts-90 mass parts in a urethane resin composition is mentioned, for example.

As the solvent (B), for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N,2-trimethylpropane Amide, N,N-dimethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacetamide, N,N-diethylacrylamide, N-ethyl Base pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, etc. These organic solvents may be used alone or in combination of two or more kinds. In addition, if necessary, ethyl acetate, methyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropanol, isobutanol, and second butyl can also be used together. Organic solvents such as alcohol and tertiary butanol.

As content of the said solvent (B), the range of 10 mass%-90 mass% in a urethane resin composition is mentioned, for example.

The urethane resin composition contains the urethane resin (A), the solvent (B) and the film-forming aid (C) as essential components, but may also contain other additive.

As the other additives, for example, pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, defoamers, dispersants, penetrants, surfactants, fillers, antifungal agents, antibacterial agents, UV absorbers, antioxidants, weathering stabilizers, fluorescent whitening agents, anti-aging agents, tackifiers, etc. These additives may be used alone or in combination of two or more kinds.

Next, the method of manufacturing a porous body by the wet film-forming method with respect to the said urethane resin composition is demonstrated.

The wet film forming method means that the urethane resin composition is coated or impregnated on the surface of the substrate, and then water or steam or the like is brought into contact with the coated or impregnated surface, thereby A method of coagulating the urethane resin (A) to produce a porous body.

As the substrate to which the urethane resin composition is applied, for example, a substrate including a non-woven fabric, a woven fabric, and a knitted fabric; a resin film, etc., can be used. As the material constituting the substrate, for example, chemical fibers such as polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, and polylactic acid fiber; cotton, hemp, Silk, wool, their blended fibers, etc.

The surface of the substrate may be subjected to electrical processing, mold release processing, water repellent processing, water absorption processing, antibacterial deodorization processing, bacteria processing, ultraviolet shielding processing, etc., if necessary.

As a method of coating or impregnating the urethane resin composition on the surface of the substrate, for example, a gravure coating method, a knife coating method, a tube coating method, and a cut-off wheel coating method can be cited. At this time, in order to adjust the viscosity of the urethane resin composition to improve coating workability, the amount of the organic solvent (B) used can be adjusted as necessary.

The thickness of the coating film including the urethane resin composition coated or impregnated by the method is preferably in the range of 0.5 mm to 5 mm, more preferably in the range of 0.5 mm to 3 mm .

As a method of bringing water or water vapor into contact with the coating surface formed by coating or impregnating the urethane resin composition, for example, a method containing the urethane resin composition may be provided. A method in which the substrate of the coating layer or the impregnation layer is immersed in a water bath; a method in which water is sprayed on the coating surface by spraying or the like. The immersion may be performed in a water bath at 5°C to 60°C for 2 minutes to 20 minutes, for example.

Preferably, the surface of the porous body obtained by the method is washed with water at room temperature or warm water, the solvent (B) is extracted and removed, and then dried. The washing may be performed with water at 5°C to 60°C for 20 minutes to 120 minutes, for example, and the water used for washing is preferably replaced once or more or continuously replaced with running water. The drying is preferably performed for 10 minutes to 60 minutes using a dryer or the like adjusted to 80°C to 120°C, for example.

As described above, according to the present invention, by using a specific film-forming aid, a fine and uniform porous body with a low compressibility can be produced by a wet film-forming method. Therefore, the present invention can be particularly suitable for the manufacture of polishing pads, artificial leather, and synthetic leather. [Example]

Hereinafter, examples are used to explain the present invention in more detail.

[Synthesis example 1] Synthesis of urethane resin (A-1) In a reaction device equipped with a stirrer, a reflux device, and a thermometer, 100 parts by mass of polyester polyol (reaction product of 1,4-butanediol and adipic acid, number average molecular weight: 2,000) and 12 parts by mass of ethylene glycol are introduced , N,N-dimethylformamide (hereinafter referred to as "DMF") 519 parts by mass and 4,4'-diphenylmethane diisocyanate 61 parts by mass, reacted at 60°C for 6 hours with stirring, and then 1 part by mass of isopropyl alcohol was added, and further stirred at 60° C. for 1 hour to obtain a urethane resin (A-1) composition. In the obtained urethane resin (A-1) composition, the solid content was 25% by mass, the viscosity was 600 dPa, and the weight average molecular weight of the urethane resin was 188,100.

[Synthesis example 2] Synthesis of urethane resin (A-2) In a reaction device with a stirrer, a reflux device, and a thermometer, 65 parts by mass of polyester polyol (the reaction product of ethylene glycol and adipic acid, number average molecular weight: 2,000), polytetramethylene glycol (number average Molecular weight: 2,000) 35 parts by mass, 20 parts by mass of 1,4-butanediol, 564 parts by mass of DMF, and 68 parts by mass of 4,4'-diphenylmethane diisocyanate, reacted at 60°C for 6 hours with stirring, and then 1 part by mass of isopropanol was added, and further stirred at 60° C. for 1 hour to obtain a urethane resin (A-2) composition. In the obtained urethane resin (A-2) composition, the solid content was 25% by mass, the viscosity: 550 dPa, and the weight average molecular weight of the urethane resin was 168,100.

[Measurement method of number average molecular weight and weight average molecular weight] The number average molecular weight of the raw material polyol used in the synthesis example and the weight average molecular weight of the urethane resin (A) represent the values measured by the gel permeation chromatography (GPC) method under the following conditions.

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) String: The following pipe strings manufactured by Tosoh Co., Ltd. are connected in series and used. "TSKgel G5000" (7.8 mmI.D.×30 cm)×1 "TSKgel G4000" (7.8 mmI.D.×30 cm)×1 "TSKgel G3000" (7.8 mmI.D.×30 cm)×1 "TSKgel G2000" (7.8 mmI.D.×30 cm)×1 Detector: RI (differential refractometer) Column temperature: 40℃ Eluent: tetrahydrofuran (tetrahydrofuran, THF) Flow rate: 1.0 mL/min Injection volume: 100 μL (a tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: The following standard polystyrene was used to prepare a calibration curve.

(Standard polystyrene) "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[Example 1] With respect to 100 parts by mass of the urethane resin (A-1) composition obtained in Synthesis Example 1, 40 parts by mass of DMF and a different chain of 12 carbon atoms as a film-forming aid were added 1 part by mass of alkane ("MERVEILLE 30" manufactured by East Asia Petroleum Co., Ltd., density: 0.77 g/cm ³ , hereinafter referred to as "c1-1"), made into a mixed solution, and made a thickness (Wet) of 1 mm coating on polyethylene terephthalate (PET) film. Next, the coated substrate was immersed in a coagulation bath (25°C water) for 10 minutes to coagulate the urethane resin. Thereafter, the substrate was immersed in water at 50°C for 60 minutes to wash the solvent. After washing, the substrate was dried with hot air at 100°C for 30 minutes to obtain a porous body.

[Example 2] In Example 1, the type of film-forming aid was replaced with isoparaffin with 12 carbon atoms ("IP Solvent 1620 (IP Solvent 1620) manufactured by Idemitsu Kosan Co., Ltd.", density; A porous body was obtained in the same manner as in Example 1 except that 0.76 g/cm ^{3 and hereinafter abbreviated as "c1-2").}

[Example 3] In Example 1, the type of film-forming aid was replaced with isoparaffin with 12 carbon atoms ("IP Clean LX (IP Clean LX) manufactured by Idemitsu Kosan Co., Ltd.", density ; 0.74 g/cm ³ , hereinafter abbreviated as "c1-3"), except that the same procedure as in Example 1 was carried out to obtain a porous body.

[Example 4] In Example 1, the type of the film-forming aid was replaced with an isoparaffin with 16 carbon atoms ("IP Solvent 2028 (IP Solvent 2028)" manufactured by Idemitsu Kosan Co., Ltd., and density; A porous body was obtained in the same manner as in Example 1 except that 0.79 g/cm ^{3 and hereinafter abbreviated as c1-4").}

[Example 5] In Example 1, except that the urethane resin (A-2) composition was used instead of the urethane resin (A-1) composition, a porous body was obtained in the same manner as in Example 1.

[Comparative Example 1] In Example 1, a porous body was obtained in the same manner as in Example 1, except that the type of the film-forming aid was replaced with hexane (hereinafter referred to as "cR1-2").

[Comparative Example 2] In Example 1, the type of film-forming aid was replaced with an isoparaffin with 20 carbon atoms ("IP Solvent 2835" manufactured by Idemitsu Kosan Co., Ltd., density; 0.82 g/cm ³ , Hereinafter, it is abbreviated as cR1-1"), except that a porous body was obtained in the same manner as in Example 1.

[Evaluation Method of Wet Film Formation] Use the scanning electron microscope "JSM-IT500" manufactured by JEOL Co., Ltd. (magnification: 100 times) to observe the cross-sectional state of the porous body obtained in the example to confirm the cell shape (fineness, uniformity), if the maximum width Units with a thickness of 70 μm or less accounted for 60% of the total and were evaluated as "○", and the other cases were evaluated as "×".

[Evaluation method of compression ratio] For the porous bodies obtained in the examples, the compression ratio was evaluated in accordance with Japanese Industrial Standards (JIS) L-1021-6. Specifically, the "thickness under standard pressure: t0" after the initial load of 2 kPa is applied for 30 seconds, and then the "thickness under constant pressure: t1" after the final load of 98 kPa is applied for 30 seconds. , Apply it to the following formula to calculate the compression ratio. Compression rate (%)=100×(t0-t1)/t0 If the compression ratio thus obtained was 20% or less, it was evaluated as "○", and the other cases were evaluated as "×".

[Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Urethane resin (A) type (A-1) (A-1) (A-1) (A-1) (A-2) (A-1) (A-1) Film forming aid (C) type c1-1 c1-2 c1-3 c1-4 c1-1 cR1-1 cR1-2 content Isoparaffin Isoparaffin Isoparaffin Isoparaffin Isoparaffin Hexane Isoparaffin Number of carbon atoms 12 12 12 16 12 6 20 Content (with respect to 100 parts by mass of urethane resin (A)) 4 4 4 4 4 4 4 Evaluation of wet film formation ○ ○ ○ ○ ○ X X Evaluation of compression ratio ○ ○ ○ ○ ○ X X

It can be seen that the porous body obtained by the urethane resin composition of the present invention has fine and uniform units, and is also excellent in low compressibility.

On the other hand, Comparative Example 1 is a form in which a hydrocarbon having a number of carbon atoms lower than the number of carbon atoms specified in the present invention is used as the film-forming aid, and the porous unit formation is poor, and the low compressibility is also poor.

Comparative Example 2 is a form in which a hydrocarbon having a carbon number higher than the number of carbon atoms specified in the present invention is used as the film-forming aid, and the porous unit formation is poor, and the low compressibility is also poor.

without

without

Claims (4)

A urethane resin composition containing a urethane resin (A), a solvent (B) and a film-forming aid (C), characterized in that: The film-forming aid (C) contains hydrocarbons (c1) in the range of 8 to 18 carbon atoms. The urethane resin composition according to claim 1, wherein the content of the hydrocarbon (c1) is 0.1 to 30 parts by mass relative to 100 parts by mass of the urethane resin (A) The range of servings. The urethane resin composition according to claim 1 or 2, wherein the hydrocarbon (c1) is an isoparaffin. A method for producing a porous body, characterized in that the urethane resin composition according to any one of claims 1 to 3 is subjected to wet film formation.