JPH01291908A - Release agent - Google Patents

Abstract

PURPOSE:To prepare a release agent of long release life and superior film forming properties and release properties by blending a highly fluorinated organic compound with a kind of fluoride including fluoroalkyl or fluoroalkenyl. CONSTITUTION:A release agent is composed of a mono-substituted ethylene containing fluoroalkyl or fluoroalkenyl, or a homologous copolymer or a mutual copolymer of (meth)acrylic acid ester, or a copolymer copolymerizable with (meth)acrylic ester, and a highly fluorinated organic compound. Said release agent is of superior film forming properties, and can form a uniform film on a molding surface of complicated shape or large size, and even a release agent of 0.1% concentration or so can exercise superior release properties to enhance the dimension accuracy of a molded product.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a mold release agent, and more particularly to a mold release agent used in the production of molded articles of polymeric substances such as synthetic resins and rubbers.

Conventional technologies and their problems In recent years, silicone oil, mineral oil, paraffin wax,
In order to eliminate the drawbacks of conventional mold release agents such as fatty acid derivatives, glycols, talc, and mica, a mixture of a fluoroalkyl group-containing phosphate ester having 4 to 20 carbon atoms or a salt thereof and silicone oil (Japanese Patent Publication No. 53-23270 (Japanese Patent Publication No. 53-23271), a mixture of a fluoroalkyl group-containing phosphate ester having 4 to 20 carbon atoms or its salt and silicone varnish (Japanese Patent Publication No. 57-48035), a fluoroalkyl group-containing polyether compound and silicon Mold release agents such as mixtures with oil etc. (Japanese Patent Publication No. 59-32513) have been developed. These are preferable mold release agents that have excellent mold release performance and have a longer mold release life than conventional ones. Furthermore, a mold release agent consisting of a fluoroalkyl group-containing phosphate ester compound and silicone oil exhibits good mold release properties when molding most polymeric substances. However, as the shapes of polymer molded articles become more complex and larger, it is necessary to further improve the performance of mold release agents, and in particular, improvement in mold release properties is desired.

Means for Solving the Problems In view of the above-mentioned problems, the present inventor has conducted intensive research and found that highly fluorinated organic The present invention was completed based on the discovery that by blending the compound, a mold release agent with a significantly longer mold release life than conventional mold release agents and excellent film-forming properties and mold release performance could be obtained.

That is, the present invention provides monosubstituted ethylene containing (A) a fluoroalkyl group or a fluoroalkenyl group;
Contains a homologous polymer or interpolymer of meth)acrylic acid ester, or a copolymer of the monosubstituted ethylene or a monomer copolymerizable with the (meth)acrylic acid ester, and (B) a highly fluorinated organic compound. "Mold release agent"
Pertains to.

Here, examples of the fluoroalkyl group include a perfluoroalkyl group and an omega hydroperfluoroalkyl group, and among these, a perfluoroalkyl group is more preferred. In addition, as a fluoroalkenyl group,
More preferred is a perfluoroalkenyl group.

In the present invention, homologous polymers of monosubstituted ethylene or (meth)acrylic acid esters containing a fluoroalkyl group or fluoroalkenyl group, interpolymers of these ethylenes and esters, or monosubstituted ethylene or (meth)acrylic acid esters, At least one copolymer with a copolymerizable monomer is used.

Examples of the monosubstituted ethylene and (meth)acrylic acid ester include compounds represented by the following general formulas (1) to (6).

RrR20COCR' -CH2(1)RfSO2NR
3R40CORICH2(2)RrO◎C00R20
COR' -CH2(3)R,O◎CH-CH2(4) Rr R2CH"" CR2(5) RrCM-CH2(6) [In the formula, Rr is a fluoroalkyl group or a fluoroalkenyl group having 4 to 20 carbon atoms , R1 is a hydrogen atom or a methyl group, R2 is an alkylene group having 1 to 10 carbon atoms or a group -CH2C
H(OR3)CH2-1 R3 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R4 represents an alkylene group having 1 to 10 carbon atoms. ] Specific examples of the fluorine-containing compounds represented by the above general formulas (1) to (5) are listed below.

CF3 (CF2) A CH20COC(CH3
) -CH2CF3 (CF2) s (CIH2)
20COC(CH3) −(j(2CF3 (CF2
) s 0COCH-CH2CF3 (CF2 )
y CH2CH20COCH=CH2CF3 CF2
(CF2 CF2)2-8 (CH2CH2)20CO
CH-CH2CH3 CF3 (CF2) 7 SO2NCH2CH20
COC(CH3) -CH2(CF3)3C(C
F2 CF2 ) 2 CH2CH20COCH-CH
2CF3 CF2 (CF2 CF2 )3 CH-
CH2 Furthermore, monomers copolymerizable with monosubstituted ethylene or (meth)acrylic acid ester containing a fluoroalkyl group or a fluoroalkenyl group include, for example, methyl, ethyl, propyl, butyl, cyclohexyl,
benzyl, octyl, 2-ethylhexyl, lauryl,
Tridecyl, cetyl, stearyl, methoxyethyl, ethoxyethyl, butoxyethyl, methoxypolyethylene glycol, 2-hydroxyethyl, 2-hydroxy-
3-taloloprobil, diethylaminoethyl, glycidyl, and tetrahydrofurfuryl (meth)acrylic acid esters, acrylamide, methacrylic acid amide, vinyl esters of monovalent organic acids with carbon atoms of 2 to 18, carbon atoms of 1 to 18 Examples include alkyl vinyl ether, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, (meth)croxypropyltrimethoxysilane, and the like.

In order to obtain a copolymer of a monosubstituted ethylene or (meth)acrylic acid ester containing a fluoroalkyl group or a fluoroalkenyl group and a monomer copolymerizable therewith, any conventional polymerization method can be employed; The conditions for the polymerization reaction can also be selected arbitrarily. Specifically, a solution polymerization method, a bulk polymerization method, a radiation polymerization method, etc. can be exemplified. For example, according to the solution polymerization method, first, a monosubstituted ethylene or (meth)acrylic acid ester containing a fluoroalkyl group or a fluoroalkenyl group, or a monomer copolymerizable with the monosubstituted ethylene or (meth)acrylic acid ester, is added. is dissolved in a suitable organic solvent or dispersed in water using an emulsifier, and then this solution or dispersion is treated with a polymerization initiator such as a peroxide, an azo compound, or ionizing radiation. You can get a combination. The organic solvent is not particularly limited, but includes, for example, methyl chloroform, tetrachlorodifluoroethane, 1.1.
2-) Lichloro 1.2.2-Halogenated hydrocarbon solvents such as 2-trifluoroethane, trichloroethylene, and tetrachloroethylene can be exemplified. The average molecular toxicity of the polymer thus obtained is about 2,000 to 60,000. In addition, the addition copolymerization ratio of monosubstituted ethylene or (meth)acrylic acid ester containing a fluoroalkyl group or fluoroalkenyl group and a monomer copolymerizable therewith is usually 80% or more of the former. preferable.

On the other hand, highly fluorinated organic compounds used in the present invention include fluorine-containing oils, fluoroolefin telomers, and fluoroalkanes. Examples include polyether oils, fluorochloroolefin telomers, and fluoroalkanes.

These highly fluorinated organic compounds are well known, and commercially available products include Demnum (manufactured by Daikin Industries), Krytox (manufactured by DuPont), and F.
Omblin (manufactured by Monte Edison), Akul
an (manufactured by Allied), etc.

The highly fluorinated organic compounds mentioned above will be explained in more detail.

(2) Fluoropolyether and fluorochloropolyether include the following (a) to (f).

(a) The main part (the part other than the terminal group) consists of 2 to 200 repeating units of -CH2CF2CF20-2, 2. 3. A polymer of 3-tetrafluorooxetane (this is disclosed in JP-A-60-137928; this is referred to as polymer (1)).

To give a specific example, a mixture F (CH2CF2CF20) of a polymer compound CF3 (p is an integer of 1 to 10) having an average molecular weight of 1.5 x 104 and consisting of repeating units of -CH2-CF2-CF2-0- (CH2CF2CF20) CH2CF2 C.O.
Mixture of OCH3 (q is an integer of 0 and 1 to 9) CH2CF2 Polymer compound 1 with an average molecular weight of 1.0XIO' consisting of repeating units of CF20- (CH2CF2 CF20) CH2CF2 C
OOCH3D is a mixture of 0 and an integer from 1 to 5) CF30F20F20 (CH2CF20F20). CH
Mixture F (CH2CF20F20) (CHCF20)nCF of 2CF2C00CH3 (n is an integer from 1 to 8)
COOCH3 (m is an integer of 2 to 9, n is a mixture of O and an integer of 1 to 3 (CF3)si CFO(CH2CF2
0). Mixture of CH2CF2 C00CH3 (n is an integer from 1 to 8) C3F70CFCF20 (CH2CF2 CF20)
Mixture (b) of pCH2CF3 (p is an integer of 1 to 10) Main part (part other than the terminal group) obtained by replacing some or all of the hydrogen atoms of polymer (1) with fluorine atoms
-CF 2 CF2 CF20- or 7CHFCP2
It has a repeating unit of CF20-, -CP 2 CF2
CF20-1-CHFCF2 CF20- and -C1
l 2 CF2 Consists of at least one repeating unit of CF20-, and the number of repeating units (degree of polymerization) is 2 to 2
00 polymer (this is disclosed in JP-A-60-2-02122).

To give a specific example, (CH2CF2 CF20) (CHFCFsi
CF20).

(p+q-average 25, p: q-7: 3, y units and arrangement of y units are rung 2.) (CF 2 CF2 CF20) (CHF CF
2 CF2 o) r(q+r-average 25, q:r-5
:1, the arrangement of y units and y units is random) F (CF2 CF2 CF20) CF2 CF3
(n-average 23) CF3 F70CF (CF3)
CF20 (CH2CF2 CF20) -(CHF
CF2 CF20) CHFCF3 (m+n-average 7
, m:n-1:4) F (CF2 CF2 CF20)2 CF2 CF3
F (CF2 CF2 CF20) CF2 CF3
(n-average 2.2) F (CF2 CF2 CF20) CF2 CF3
(n-average 25) (c) obtained by replacing some or all of the hydrogen atoms of polymer (1) with chlorine atoms, the main part (parts other than the terminal group) is -CCI2 CF2 CF20- or -CHCICP
2 CF20-, having a repeating unit of -CCI2 CF
2 CF20-1-CIICICP 2 CF20- and -C112CF2 A polymer comprising at least one repeating unit of -C112CF2 CF20- and having a number of repeating units (degree of polymerization) of 2 to 200 (this is disclosed in JP-A-61-113616
(disclosed in the publication).

Polymer (1) is obtained by replacing some or all of the hydrogen atoms with fluorine atoms and chlorine atoms, and the main part (other than the terminal group) is -CF2CF2CF20-1-CFCI
CP 2 CF20- or -CIIFCP2 CF2
0-1 and -CC12CF2 CF20- or -C
ICICF 2 has a repeating unit of CF20-, and -C
F2CF2CF20-1-CFCICP2C
F20-1-CIIFCP2 CF20-2-CCh
CF2 CF20-1-CHCICP2 CF20-
A polymer consisting of at least one repeating unit of and -CH2CF2CF20- and having a number of repeating units (degree of polymerization) of 2 to 200.
(disclosed in the publication).

A specific example is F (CHC9CF2 CF2'O) CHC9CF
3 (n is average 5) F (CC&!2 CF2 CF
20) CC92CF3 (n is average 5) F (C
C92CF2 CF20) CCQ2 CF2 CQ
(n is average 25) CCQ2FCF2CF20CCQ
2CF2CF2oCCQ2CF3F CCCQ F
CF2 CF20) CCQ F CF3
(n is 5 on average, xy n
xyx+y-2, x:y-1:4) F (CF2 CF2 CF20) (CC9Fe
F2 CF20) -X
yCF2CF2COF (x+y-average 20, x:y-2:l, X units and y
The arrangement of units is random) F (CF2 CF2 CF20) (CC9Fe
F2 CF20) CF2 CF3X
y(x+y-average 20, x:y-2
:1, the arrangement of X units and y units is random) (d) The main part (other than the terminal group) is -CF (CF3
) A polymer having a number of repeating units (degree of polymerization) of hexafluoro-1,2-epoxypropane consisting of repeating units of CP 20- from 10 to 100.

To give a specific example, P CCP(CF 3 ) CF 20 ] n CII
FCP 3 (n is average 50) (for example, trademark “Kr
ytox 143AD”).

(e) The main part (the part other than the terminal group) is -CF(CF3
) A polymer consisting of 4 to 50 repeating units of CP 20- and -CF 20-, and having a total number of repeating units of hexafluoro-1,2-epoxypropane and difluoro rubenoxy groups (degree of polymerization) of 8 to 100.

To give a specific example, P [CF(CP 3 )CF 20 ]n (CP
20)! II CF3 (n is 15 on average, m is 6 on average) (
For example, there is a commercially available product under the trademark "Fomblin Y25").

(f) The main part (other than the terminal group) is -CF2CF
A polymer having a number of repeating units (degree of polymerization) of 7 to 100 of tetrafluoroethane consisting of 20 repeating units.

To give a specific example, F(CF2 CF20)n CF
3 (n is 25 on average).

(2) Telomers of fluorochloroolefin include the following (g).

(g) The main part (part other than the terminal group) is -CP 2 C
A telomer having 3 to 20 repeating units of chlorotrifluoroethane (telomeri degree) consisting of repeating units of F2 CI-.

A specific example is CQ (CF20P CQ )n CQ (n is 6 on average).

■ The telomers of fluoroolefins include the following (h,
).

(h) The main part (part other than the terminal group) is -CP 2 C
A telomer having a number of repeating units (telomeri degree) of tetrafluoroethylene consisting of F2- repeating units from 2 to 50.

To give a specific example, II (CF2 CF2 ) n
CF3 (n is 6 on average), ((CF3) 2CF (CF2) n) 2
(n is 3.5 on average), CQ (CF2 CF2 )
nCl1l'2 (n is 6 on average), etc.

(2) Specific examples of aluroalkanes include the following.

(CF3) 2 CF (CF2)! CF (
CF3) 2 (b, p.

207°C) (b, p, 225°C) The highly fluorinated organic compound in the present invention, whether liquid or solid, has a boiling point of 180°C.
It is necessary that the temperature is above 200°C, and preferably 200°C or above. The mold release agent of the present invention is used in a form dissolved or dispersed in an organic solvent or an aqueous medium, but when the boiling point is less than 180°C, volatilization of the solvent or medium is prevented.

In the present invention, a homologous polymer or interpolymer of monosubstituted ethylene or (meth)acrylic acid ester containing the above-mentioned fluoroalkyl group or fluoroalkenyl group, or a monomer copolymerizable with the monosubstituted ethylene or (meth)acrylic acid ester The blending ratio of at least one type of copolymer with a highly fluorinated organic compound can be selected from a wide range of 99=1 to 1:99 in terms of weight ratio. In order not to impair film properties and mold release performance, the ratio is preferably about 95:5 to 10:90, preferably about 70:30 to 30:70.

When performing a mold release treatment using the mold release agent of the present invention, first the mold release agent of the present invention is dissolved or dispersed in an organic solvent or an aqueous medium, and then the resulting solution or dispersion is used, for example, in the mold release agent. It may be applied to the inner surface of the mold by spraying on the mold surface, brushing the mold surface, or immersing the mold in the solution or dispersion. Examples of organic solvents used include benzene,
Aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, butanol, propatool and isoproptool, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and ethyl acetate, dioxane and tetrahydrocarbons. Ethers such as furan and cellosolve, methyl chloroform, tetrachlorodifluoroethane, 1.1.2-trichloro-1,2
, 2-) halogenated hydrocarbons such as lifluoroethane, trichloroethylene, and tetrachloroethylene, nitriles such as acetonitrile, dimethylformamide, meta-xylene hexafluoride, and the like.

These organic solvents can be used alone or in combination. When producing an organic solvent solution or aqueous dispersion of the mold release agent of the present invention, the concentration of the mold release agent is usually 0.01 to 40
The amount may be about 0.07 to 3% by weight, preferably about 0.07 to 3% by weight. If a propellant such as dichlorodifluoromethane, monofluorotrichloroethane, or dichlorotetrafluoroethane is added to a solution or dispersion of the mold release agent of the present invention and aerosolized, mold release treatment can be simplified by spray treatment.

In the present invention, various surfactants such as cationic, anionic, and nonionic surfactants may be used as necessary to improve the stability and wettability of the mold release agent, and also to improve mold release properties and lubricity. For the purpose of improvement, fluororesin powder, fluorocarbon, aluminum powder, copper powder, mica powder, silicone oil, silicone varnish, etc. may be added. Furthermore, a film forming agent, a viscosity modifier, etc. may be added as necessary.

The mold release agent of the present invention can be used for any ordinary polymer molding, for example, for molding rubber, thermoplastic resin, thermosetting resin, fiber-reinforced synthetic resin, and other inorganic moldings. It is valid. Furthermore, the mold release agent of the present invention is particularly effective for molding resins that easily react with conventional mold release agents such as epoxy resins, rubbers such as urethane foam, and the like.

The mold release agent of the present invention can also be used as a back treatment agent, an antiblock agent, etc.

Effect of the invention The mold release agent of the present invention exhibits the following excellent effects.

(1) The mold release agent of the present invention has excellent film-forming properties and can form a uniform coating film on the surface of a mold with a complex shape or a large size.

(2) Since excellent mold release properties are exhibited even with a mold release agent concentration of 0.1%, the dimensional accuracy of the molded article is improved.

(3) It has excellent mold releasability, and is particularly effective as a mold release agent for peroxide vulcanized rubber. Therefore, by using the mold release agent of the present invention, productivity is significantly improved.

EXAMPLES Examples and comparative examples are given below to make the present invention even clearer. If it is simply referred to as "part" or "%" below,
Each represents "part by weight" or "% by weight."

Example 1 1 Purpose The mold release agent of the present invention and the conventional mold release agent were subjected to a mold release test for epoxy resin, semi-rigid urethane foam, and fluororubber, and
The mold release performance and mold release life were measured.

2 Release agent used (A) Production of polymer 1) Polymer ■, ■, ■ Glass autoclave equipped with a stirrer (inner volume IQ
), 400 g of 1,1.2-)lichloro1゜2.2-)lifluoroethane, 4 g of t-butyl peroxybivalate, and a polymerizable compound having the following composition (■, ■, ■)
130 g of the solution was added, and an addition polymerization reaction was carried out at 48° C. for 8 hours with stirring to produce polymers having the compositions ①, ②, and ②, respectively.

2) Polymer ■ Into a glass autoclave similar to the above, 20 g of propylene glycol monomethyl ether and 100 g of a polymerizable compound (■) having the following composition were placed, stirred and heated,
When the temperature became constant at 110°C, 2 g of t-butylperoxyisopropyl carbonate was added, and an addition polymerization reaction was carried out at 110°C for 4 hours to produce a polymer having the composition (2).

(CH30) s S i CH2CH20COC(C
H3) -CH22%CH3(CH2)+ e C0
0CH-CH220% by weight 2H5 CF3 (CF2) 7 SO2NCH2CH20C
OCH-CH295rM%■ HOCH2CH20COCH-CH25% by weight [However ■
The fluorine-containing compound composition of and
The mol% is 4 mol% for n=6 and 1 mol% for n=7. ] (B) The mold release agent polymers of the present invention (1) to (2) and the fluorine-containing polyether oils and solvents shown in (1) to (3) below are blended in the proportions shown in Table 1, and 1.
After stirring and mixing for 0 minutes, mold release agents Nos. 1 to 13 were obtained.

■ F (CF20F20F20) CF20F3n#26 CF3 ■ F (CFCF20) CHFCF3 n#30 CF3 ■ F (CFCF20) (CF20) CF3I
1 n=25. m-10 ■ C9 (CF2 CFC9) CQn-3 to 12 In the column of solvent in Table 1, IPA represents isopropyl alcohol and S-3 represents 1,1,2-trifluorotrichloroethane. (The same applies hereinafter) (C) Conventional mold release agent Table 2 shows conventional mold release agents used as comparative examples.

3 Mold release test of semi-rigid urethane foam (A) Composition of semi-rigid urethane foam A liquid Sumisen 3900 (polyol) 90 parts water
(Blowing agent) 1.6 parts Triethanolamine (Catalyst) 3 parts Triethylamine (Catalyst) 0.5
Part Kaolizer (foam stabilizer) 0.5 parts B liquid Sumidur 44V20 (Isocyanate) 41.3
Part (B) Test method Various mold release agents were applied to a 6 cm x 3 cm aluminum mold, heat treated and dried. Next, the semi-rigid urethane foam liquids A and B were stirred and mixed at 5000 rpm x 10 seconds, and immediately poured into the aluminum mold.

After curing at room temperature for 10 minutes, a tensile tester (tensile speed 2
00 mm/min) to determine the mold release performance based on the adhesive strength. The values of ``mold releasability'' in Table 3 are the judgment values of the most average releasability during measurement.

Table 3 Table 3 (Continued) 4 Epoxy resin mold release test: (A) Composition of epoxy resin A liquid Epicoat #828 (manufactured by Shell Chemical) 100 parts B liquid triethylenetetramine 10 parts (B) Test method 1010X10 A mold release agent was brushed onto the aluminum mold and air-dried. Next, the above epoxy resins A and B were thoroughly mixed, impregnated into a glass fiber cloth (Chop Strand Mat, Nitto Boseki ■) measuring 10 cm x 10 cm, and then poured into a mold.

After being cured for one day at 25°C, it was tested at 90° using a tensile tester (tensile speed 20ml++/min).
The mold release performance was measured by peel strength. The mold release life was defined as the period after applying the mold release agent once until the mold releasability deteriorated without further application. That is, the molding is repeated without applying a mold release agent until the molded product can be taken out in a perfect shape, and the number of times the molded product can be taken out in a perfect shape is defined as the mold release life. The mold releasability values in Table 4 are the most average determination values of mold releasability during measurement.

Floor 4 Table 5 Release test of fluororubber (A) Compounding composition of fluororubber Daiel G901 [manufactured by Daikin Industries, Ltd.] 100 parts MT carbon black (R,T, manufactured by Vanderbilt Co Inc.)
20 parts Perhexa 2.5B [manufactured by NOF ■] 1゜5 parts triallylisocyanurate [manufactured by Nippon Kasei ■] 4 parts (B) Vulcanization conditions Vulcanization pressure 35 kg/cm2 Vulcanization temperature
160℃ Vulcanization time 1 part CC') Test method Release agent was applied with a brush to an unplated steel mold at room temperature. After air drying,
Twenty rubber plates with a diameter of 40++ on and a thickness of 2 m1II were vulcanized and molded, and the mold releasability was measured using the following criteria.

6: It lifts up from the mold 5: It can be easily removed by hand 4: It can be removed with light pressure 3: It can be removed with some force 2: It is difficult to remove from the mold 1: It cannot be removed due to adhesion After applying the molding agent once, it was measured by the number of times until the mold releasability deteriorated. That is, the molding was repeated without applying a mold release agent until the molded product could be taken out in a perfect shape, and the number of times the molded product could be taken out in a perfect shape was defined as the mold release life. The mold releasability values in Table 5 are the most average determination values of mold releasability during measurement.

From the results shown in Table 5, it can be seen that the mold release agent of the present invention has a significantly superior mold release life compared to conventional mold release agents, and is also superior in mold release performance and secondary processability.

(that's all)

Claims (1)

[Scope of Claims] [1] (A) A homologous polymer or interpolymer of monosubstituted ethylene or (meth)acrylic acid ester containing a fluoroalkyl group or a fluoroalkenyl group, or the monosubstituted ethylene or (meth)acrylic acid ester A mold release agent comprising a copolymer of an acid ester and a copolymerizable monomer and (B) a highly fluorinated organic compound. [2] Claim 1, wherein the highly fluorinated organic compound is at least one of a fluoropolyether, a fluorochloropolyether, a fluoroolefin telomer, a fluorochloroolefin telomer, and a fluoroalkane. The mold release agent described in .