JPH05169460A - Release agent composition - Google Patents

Abstract

PURPOSE:To obtain a release agent composition capable of simply and certainly performing the demolding of a low-foamed polyurethane molded object by mixing a copolymer of specific polyfluoroalkyl acrylate and a vinyl compound and wax in a specific ratio. CONSTITUTION:A release agent composition is constituted of 1-99wt.% of a specific copolymer and 99-1wt.% of wax. The specific copolymer is constituted of polyfluoroalkyl acrylate or methacrylate having a 1-20C polyfluoroalkyl group and a vinyl compound having a 8-30C alkyl group. Further, the copolymer is set to 20-70wt.% and wax is set to 80-30wt.%. The composition of the copolymer consists of 20-85wt.% of ester and 80-15wt.% of the vinyl compound. This release agent composition is used in low-foamed polyurethane.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a release agent composition,
More specifically, the present invention relates to a mold release agent composition suitable for use in molding a molded product such as a synthetic resin or a synthetic rubber, particularly a low-foamed polyurethane molded product.

[0002]

2. Description of the Related Art When molding a molded product of synthetic resin such as acrylic resin, epoxy resin, urethane resin, vinyl chloride resin, vinyl acetate resin or a molded product of synthetic rubber, it is easy to release the molded product from the molding die. In order to achieve the above, a release agent is applied to the inner surface of the molding die.

Wax-based release agents such as paraffin wax, ester wax of higher fatty acid, and polyethylene wax are known as release agents used in such cases. These wax-based release agents have been widely used since they are available at low cost and the surface condition of the resulting molded products is good. However, since wax-based mold release agents are inferior in mold release force, it is sufficient to apply a thick coat to the mold, especially when molding molded products using materials with strong adhesive force such as epoxy resin and urethane resin. However, there is a problem in that the inside of the molding die is contaminated as the number of molding steps is repeated. This problem also adversely affects the dimensional accuracy of the molded body.

Further, since the wax-based mold release agent also has poor adhesion to the molding die, it has a problem that it easily transfers to the surface of the molded product and the durability of the mold release effect is poor. This problem also leads to the problem that a release agent must be formed in each molding process. Furthermore, since the wax-based release agent transfers to the surface of the molded product in large quantities when the molded product is released from the molding die, secondary processability (printing, coating) on the surface of the molded product
It is inferior to.

As a solution to these problems, a fluorine-based releasing agent [a copolymer of a polyfluoroalkyl ester of (meth) acrylic acid and a substituted vinyl compound]
Is known (see Japanese Patent Laid-Open No. 60-255404). Since this fluorine-based releasing agent has an excellent releasing force, a sufficient releasing effect can be obtained only by forming it thin. Further, the adhesive force to the molding die is also superior to that of the above wax-based release agent, and therefore the durability of the release effect is also excellent.

[0006]

However, even with the above-mentioned fluorine-based mold release agent, the transfer to the surface of the molded article cannot be completely avoided, and if this transfers to the surface of the molded article, It adversely affects the secondary processability (printing, coating) on the surface. This is because the fluorine-based release agent transferred to the surface of the molded body
This is because it also exhibits releasability against ink and paint when printing and applying. A release agent composed of a copolymer obtained by polymerizing a perfluoroalkyl group-containing vinyl monomer, a phosphoric acid-containing vinyl monomer and a hydrocarbon vinyl monomer (see Japanese Patent Publication No. 3-8245). Also, a release agent (Japanese Patent Publication No. 59-32514) prepared by blending a polyfluoroalkyl group-containing copolymer with a silicone resin is known. However, these mold releasing agents also have a problem in the secondary workability on the surface of the molded product, or the mold releasing property is unsatisfactory.

[0007]

In order to improve the drawbacks of the above-mentioned fluorine-based mold releasing agent, the present invention provides A) a polyfluoroalkyl acrylic acid ester or methacrylic acid having 1 to 20 carbon atoms in the polyfluoroalkyl group. Provided is a release agent composition comprising 1 to 99% by weight of a copolymer of an acid ester and a vinyl compound having an alkyl group having 8 to 30 carbon atoms, and B) 99 to 1% by weight of a wax.

The release agent composition of the present invention, when applied to the inner surface of a molding die, may differ due to the difference in melting temperature of both components.
It is divided into a layer mainly composed of A component and a layer mainly composed of B component,
The component A mainly fulfills the function of adhering to the molding die, and the component B mainly fulfills the effect of releasing from the molding. Further, the vinyl compound having an alkyl group having 8 to 30 carbon atoms which is copolymerized in the component A also has an effect of keeping the component B bound by the long chain alkyl group. That is, A on the molding die side
A layer mainly composed of the component is formed, a layer mainly composed of the component B is formed on the side of the molded product, and the layer mainly composed of the component A does not transfer to the surface of the molded product when the molded product is released from the mold. The layer mainly composed of is transferred. Moreover, in this case, the amount of transfer of the layer mainly composed of the component B is smaller than the amount of transfer when the wax-based release agent is used alone. Does not adversely affect workability.

Examples of the polyfluoroalkyl acrylic acid ester or methacrylic acid ester preferably used in the present invention are represented by the general formula: CH ₂ ═CR ¹ COOR ² Rf [wherein R ¹ is a hydrogen atom or a methyl group, R ² Is 1-10
Pieces linear or branched alkylene group having carbon atoms ^{_{of, -SO 2 N (R 3)}} R 4 - ^{_{group, CH 2 CH (OR 5)}} CH 2 -
A group (provided that R ³ is an alkyl group having 1 to 10 carbon atoms, R ⁴ is a linear or branched alkylene group having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or 1 to It is an acyl group having 10 carbon atoms.), Rf is 1 to 20.
Represents a straight-chain or branched polyfluoroalkyl group having 4 carbon atoms. ] It is a compound shown by these.

Specific examples of such compounds include the following. _{CF 3 (CF 2) 7 (} CH 2) 10 OCOCH = CH 2 CF 3 (CF 2) 7 (CH 2) 10 OCOC (CH 3) = CH 2 CF 3 (CF 2) 6 CH 2 OCOCH = CH 2 CF _{3 (CF 2) 6 CH 2} OCOC (CH 3) = CH 2 (CF 3) 2 CF (CF 2) 6 (CH 2) 2 OCOCH = CH 2 (CF 3) 2 CF (CF 2) 8 (CH 2 _{) 2 OCOCH = CH 2 (CF} 3) 2 CF (CF 2) 10 (CH 2) 2 OCOCH = CH 2 (CF 3) 2 CF (CF 2) 6 (CH 2) 2 OCOC (CH 3) = CH 2 _{(CF 3) 2 CF (CF} 2) 8 (CH 2) 2 OCOC (CH 3) = CH 2 (CF 3) 2 CF (CF 2) 10 (CH 2) 2 OCOC (CH 3) = CH
_{2 CF 3 CF 2 (CF 2} ) 6 (CH 2) 2 OCOCH = CH 2 CF 3 CF 2 (CF 2) 8 (CH 2) 2 OCOCH = CH 2 CF 3 CF 2 (CF 2) 10 (CH 2) _{2 OCOCH = CH 2 CF 3 CF} 2 (CF 2) 6 (CH 2) 2 OCOC (CH 3) = CH 2 CF 3 CF 2 (CF 2) 8 (CH 2) 2 OCOC (CH 3) = CH 2 CF _{3 CF 2 (CF 2) 10} (CH 2) 2 OCOC (CH 3) = CH 2 H (CF 2) 8 CH 2 OCOC (CH 3) = CH 2 H (CF 2) 8 CH 2 OCOCH = CH 2 Cl _{(CF 2 CF 2) 3 CH} 2 OCOCH = CH 2 Cl (CF 2 CF 2) 3 CH 2 OCOC (CH 3) = CH 2 CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 2 OCOCH = C
_{H 2 CF 3 (CF 2)} 7 SO 2 N (C 2 H 5) (CH 2) 2 OCOC (C
_{H 3) = CH 2 (CF} 3) 2 CF (CF 2) 8 CH 2 CH (OCOCH 3) CH 2 O
_{COC (CH 3) = CH 2} (CF 3) 2 CF (CF 2) 8 CH 2 CH (OH) CH 2 OCOCH
_{= CH 2 CF 3 CF 2 (} CF 2 CF 2) nCH 2 CH 2 OCOCH = CH 2
(N = mixture of 3-5 compounds)

An example of a compound preferable as a vinyl compound having an alkyl group having 8 to 30 carbon atoms is represented by the general formula: CH ₂ ═CR ¹ COOR ⁶ CH ₂ ═CHOR ⁶ CH ₂ ═CHOCOR ⁶ CH ₂ ═CHR ⁶ [ In the formula, R ¹ has the same meaning as above. R ⁶ represents an alkyl group having 8 to 30 carbon atoms, an aralkyl group, an alkenyl group, or an alkyl group, an aralkyl group, or an alkenyl group substituted with a hydroxyl group or a carboxyl group. ].

Specific examples of such compounds include the following. _{CH 2 = CHCOOC 8 H 17 CH} 2 = CHCOOC 10 H 21 CH 2 = CHCOOC 12 H 25 CH 2 = CHCOOC 18 H 37 CH 2 = CHCOOC 22 H 45 CH 2 = C (CH 3) COOC 8 H 17 CH 2 = _{C (CH 3) COOC 10 H} 21 CH 2 = C (CH 3) COOC 12 H 25 CH 2 = C (CH 3) COOC 18 H 37 CH 2 = C (CH 3) COOC 22 H 45

[0013]

[Chemical 1]

CH ₂ ═CHCOOCH (C ₆ H ₁₃ ) (CH ₂ ) ₁₀ COOH CH ₂ ═CHCOOCH ₂ CH (OH) CH ₂ OC ₁₈ H ₃₇ CH ₂ ═CHOC ₈ H ₁₇ CH ₂ ═CHOC ₁₀ H ₂₁ CH _{2 = CHOC 12 H 25 CH 2 =} CHOC 16 H 33 CH 2 = CHOC 18 H 37 CH 2 = CHOCOC 8 H 17 CH 2 = CHOCOC 9 H 19 CH 2 = CHOCOC 11 H 23 CH 2 = CHOCOC 15 H 30 CH 2 = _{CHOCOC 17 H 35 CH 2 = CHOCO} (CH 2) 10 CH (OH) C 6 H 13 CH 2 = CHOCO (CH 2) 7 CH = CHCH 2 CH (OH)
_{C 6 H 13 CH 2 = CHC} 9 H 19

The proportion of polyfluoroalkyl acrylic acid ester or methacrylic acid ester in the copolymer is preferably 20% by weight to 85% by weight, more preferably 30% by weight to 70% by weight. If the amount is less than 20% by weight, the sufficient effect cannot be obtained and the mold stains increase. Also, 85
If the content exceeds 10% by weight, the releasability deteriorates.

The polyfluoroalkyl group has 1 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 carbon atoms.
It is -20, and if it is longer than this, it is economically unsuitable.
The carbon number of the alkyl group of the vinyl compound having an alkyl group is 8 to 30, preferably 14 to 30,
When the amount is less, sufficient releasability cannot be obtained, and the effect of the wax to hold the wax in the copolymer is weakened, and the wax is transferred to the molded body so much that the secondary processability is deteriorated. If it is more than 30, it is difficult to obtain and industrially unsuitable.

These copolymers are for the purpose of improving the film-forming property and durability of the coating film, in addition to the polyfluoroalkyl acrylic acid ester or methacrylic acid ester and the vinyl compound having an alkyl group having 8 to 30 carbon atoms. Other vinyl compounds such as butyl methacrylate, ethyl methacrylate, glycidyl methacrylate, 2-hydroxy methacrylate, styrene, cyclohexyl methacrylate, etc. may be copolymerized. However, the proportion of these other vinyl compounds is preferably 10% by weight or less in the copolymer. If it is more than this, the releasability is adversely affected.

To obtain the copolymer in the present invention,
Various polymerization methods and conditions can be arbitrarily selected, and various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and radiation polymerization can be adopted.

As the wax according to the present invention, paraffin wax, ester wax of higher fatty acid, polyethylene wax, isoparaffin wax, polyolefin wax, higher aliphatic alcohol, higher fatty acid, montan wax, carnauba wax and the like can be used.

The release agent composition of the present invention comprises a polyfluoroalkyl acrylic acid ester or methacrylic acid ester having a polyfluoroalkyl group having 1 to 20 carbon atoms and a vinyl compound having an alkyl group having 8 to 30 carbon atoms. It consists of a copolymer and a wax, and the component ratio of the copolymer and the wax is 1 to 99% by weight of the copolymer and 9% by weight of the wax.
9 to 1% by weight, preferably 10 to 90% copolymer
% By weight, 90 to 10% by weight of wax, more preferably 20 to 70% by weight of copolymer and 80 to 80% by weight of wax.
30% by weight is good. This is because when the wax is low,
The amount of the copolymer transferred to the molded product increases, which adversely affects the secondary processability of the molded product. Further, when the amount of the copolymer becomes small, a sufficient releasing property cannot be obtained unless a large amount of the releasing agent is used, which also adversely affects the secondary processability of the molded product.

When the release agent composition of the present invention is applied to a molding die, any application method such as brush coating, dip coating or spray coating is possible. When applied to these molding dies, the release agent composition of the present invention is preferably dissolved or dispersed in water or an organic solvent. After coating, it only needs to be dried. Alternatively, a propellant such as liquefied petroleum gas or 1,1,1,2-tetrafluoroethane may be used and used as an aerosol type.

The release agent composition of the present invention has good solubility in various organic solvents, and in particular, the copolymer has 8 to 30 carbon atoms.
When a vinyl compound containing 15% by weight or more of a vinyl compound having an alkyl group is used, a compound which is conventionally dissolved only in a fluorine-based, chlorine-based, or fluorohydrocarbon-based organic solvent is an ester. It is also soluble in organic solvents such as petroleum-based and petroleum-based ones, and has a feature that the selection range of the solvent is expanded. The concentration of the release agent composition in water or an organic solvent is generally 0.01 to 10% by weight, preferably 0.1 to 3% by weight.

[0023]

EXAMPLES The following examples are given to illustrate the present invention in more detail. Example 1 Copolymer (1) CF ₃ CF ₂ (CF ₂ CF ₂ ) nCH ₂ CH ₂ OCOCH = CH ₂ 70 wt% (5: 3: 1 mixture by weight of compounds of n = 3,4,5) (2) C ₁₈ H ₃₇ OCOCH = CH ₂ 30 wt% 3 parts by weight of the copolymer having the above composition, paraffin wax a1
When a release agent composition consisting of 1 part by weight and 96 parts by weight of isooctane was subjected to a release test, the results shown in Table 3 were obtained. Further, in order to evaluate the secondary workability on the surface of the molded body, a coating test of the molded body was conducted. The results are shown in Table 3.

Examples 2 to 14 The release agent compositions shown in Table 1 were subjected to a release test and a coating test. The results are shown in Table 3.

Comparative Examples 1 to 9 The release agent compositions shown in Table 2 were subjected to a release test and a coating test. The results are shown in Table 3.

[Release Test] (1) A 6 cmφ × 1 cm aluminum mold was brush coated with a release agent. (2) Urethane having the following composition was thoroughly stirred with a mixer and then poured into the mold of (1). (3) After being cured at room temperature for 10 minutes, the releasability was determined by pulling a pin that had been stood in the molded body in advance. 1 ... Releases without applying much force. 2 ... Releases the mold when a little force is applied. 3 ... It will not release if you do not apply much force. 4 ... Do not release.

[Coating Test (Crosscut Test)] (1) The following primer coating was applied by brush onto the molded product that was released in the release test. (2) After drying at 80 ° C for 10 minutes, a cross-cut test was conducted. (3) Further, the following top coating material was applied by brush onto this. (4) After drying at 100 ° C. for 40 minutes, a cross-cut test was conducted. Urethane composition Polyether polyol having a hydroxyl value of 28.1 100 parts by weight Ethylene glycol 19 parts by weight Trichlorofluoromethane 5 parts by weight Amine-based catalyst 0.9 parts by weight Dibutyltin dilaurate 0.025 parts by weight Diphenylmethane diisocyanate 104 parts by weight

Coating (manufactured by Dainippon Paint Co., Ltd.) Primer Planit L # 75 100 parts by weight Planit L # 75 thinner 100 parts by weight Topcoat Planit S 100 parts by weight Planit thinner # 10 100 parts by weight

[0029]

[Table 1]

[Table 2]

[0030]

[Table 3]

[Table 4]

[0031]

[Table 5]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location B29K 105: 04

Claims (4)

[Claims] 1. A) Copolymers 1 to 99 of a polyfluoroalkyl acrylic acid ester or methacrylic acid ester having a polyfluoroalkyl group having 1 to 20 carbon atoms and a vinyl compound having an alkyl group having 8 to 30 carbon atoms. %, And B) 99-1% by weight of a wax, a release agent composition. 2. The release agent composition according to claim 1, wherein the composition of the copolymer and the wax is 20 to 70% by weight of the copolymer and 80 to 30% by weight of the wax. 3. The composition of the copolymer is such that the polyfluoroalkyl group has 20 to 85% by weight of polyfluoroalkyl acrylic acid ester or methacrylic acid ester having 1 to 20 carbon atoms and 8 to 30 carbon atoms. The release agent composition according to claim 1 or 2, wherein the vinyl compound has 80 to 15% by weight. 4. A low-foam polyurethane product for use in low-expansion polyurethane.
The release agent composition according to any one of 3 above.