JP2001038740A - Elastic molding die - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a molding die which is free from its deformation even when it is repeatedly used and is highly durable and pliable and further, is oil-resistant by using the molding die made of a resin containing a fluoroelastomer with a specific fluorinated polyester skeleton. SOLUTION: A fluoroelastomer which becomes a material for an elastic molding die is an elastic resin material obtained by polymerizing (A) an amide compound containing fluorine represented by formula I (wherein, R1 and R2 are a univalent hydrocarbon group) and (B) an organohydrogen siloxane containing fluorine. In the formula I, Q is formula II or formula III. (In the formula II, R3 is a divalent hydrocarbon group in which one or two kinds or more selected from an oxygen atom, a nitrogen atom or a silicon atom may be made to intervene.) (In the formula III, R4, R5 are a divalent hydrocarbon group.) (In the formula I, Rf is a perfluoroalkylene group; and a is an integer of 0 or higher). The elastic molding die thus obtained is highly pliable, oil- resistant and durable and further, can be repeatedly used many times, so that the molding die is suitable for molding an oily solid decorative material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an elastic mold,
More specifically, the present invention relates to an elastic mold made of a resin containing a fluoroelastomer having a specific fluorinated polyether skeleton and a method for producing a molded article using the elastic mold.

[0002]

2. Description of the Related Art Molds made of elastic materials such as natural rubber, chloroprene rubber and silicon rubber are used in place of various widely used molded products in place of metal molds conventionally used widely.
That is, a method of molding using an elastic mold is known. In this molding method, a fluid molding material is filled into the molding from the opening of the elastic molding die, and then the molding material is solidified by heating or cooling, and the solidified molding is subjected to the elastic molding die. It is a method of taking out. In this elastic molding method, the elastic molding die is expanded by using an air pressure difference or the like, the molded product is peeled from the mold, and the elastic molding die is taken out by discharging from the expanded opening. Used repeatedly while expanding and contracting many times.

[0003] In this elastic molding method, the production cost of the molding die is low, and there is no need to consider the reverse taper or draft for releasing, so that molded products of various desired designs can be obtained. Can be made, and since there is no mold mark on the surface as in the case of molding with a split mold and the appearance is not impaired,
It is used for molding chocolate, cheese, jelly, kamaboko, and the like, and has recently been used for solid cosmetics.

However, in the case of solid cosmetics containing oily components such as lipstick and powder stick (hereinafter referred to as "oily solid cosmetics"), since they contain oily components, they are repeatedly used in conventional elastic molding dies. During this time, there is a problem that the elastic mold expands due to the oily component and the mold collapses. In particular, in the case of an oily solid cosmetic containing a large amount of oily components such as lipstick, the elastic molding die expands remarkably, not only being more easily deformed, but also having a sufficient surface gloss, which is an important quality for lipstick. There was a disadvantage that it could not be done.

More specifically, elastic molds of materials such as natural rubber, chloroprene rubber, and silicone rubber, which have been used in the past, have low oil resistance. It absorbs oily components and gradually expands, causing it to lose its shape. Then, this expansion causes the inner surface of the elastic mold to become rough, which causes a problem that the surface gloss of the molded article is lost.

Recently, a fluoro rubber such as polytetrafluoroethylene has been used as an elastic mold having excellent oil resistance. However, an elastic mold made of fluoro rubber has high hardness and flexibility. For this reason, there is a problem that the molded product is difficult to peel off from the mold and the surface gloss is impaired.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made under such circumstances, and can mold molded articles such as glossy oily solid cosmetics. It is an object of the present invention to provide an elastic mold having excellent oil resistance, durability and flexibility.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have achieved the above object by using an elastic mold made of a resin containing a fluoroelastomer having a specific fluorinated polyether skeleton. They have found out what they can do and have completed the present invention based on these findings.

That is, the present invention relates to a fluorine-containing amide compound represented by the following formulas (A), (B) and (A):

Embedded image [Wherein, R ¹ and R ² are monovalent hydrocarbon groups, and Q is the following formula (2) or (3);

Embedded image (Here, R ³ represents a divalent hydrocarbon group which may have one or more oxygen atom, nitrogen atom or silicon atom in the bond) or

Embedded image (Where R ⁴ and R ^{5 each} represent a divalent hydrocarbon group), Rf represents a divalent perfluoroalkylene group or the like, and a represents an integer of 0 or more.) (B) One molecule Having one or more monovalent perfluorooxyalkyl groups, monovalent perfluoroalkyl groups, divalent perfluorooxyalkylene groups or divalent perfluoroalkylene groups, and having two or more hydrosilyl groups An elastic mold formed of a resin containing a fluoroelastomer obtained by polymerizing a fluorine-containing organohydrogensiloxane, and a method of molding an oil-based solid cosmetic using the elastic mold.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The fluoroelastomer used as the material of the elastic molding die of the present invention comprises (A) a fluorinated amide compound represented by the above general formula (1), and (B) one or more monovalent perfluorooxy groups per molecule. Polymerizing a fluorine-containing organohydrogensiloxane having an alkyl group, a monovalent perfluoroalkyl group, a divalent perfluorooxyalkylene group or a divalent perfluoroalkylene group and having two or more hydrosilyl groups. Is an elastic resin body obtained by

[0012] The elastic resin body is preferably prepared by, for example, adding the above (A) and (B) to hydrosilyl (Si-H) in an amount of (B) per mole of the aliphatic unsaturated group in the composition. ) Can be suitably obtained by polymerizing a mixture of the groups in an amount of 0.5 to 5 mol and curing the mixture (hereinafter abbreviated as curing). As a curing method, for example, a method of adding a catalytic amount of a platinum group compound to the mixture of the above (A) and (B) and then heating the mixture can be used.

The details of the components (A) and (B) used in the preparation of the fluoroelastomer used in the present invention and details of the curing method thereof are described in JP-A-8-199070. The fluoroelastomer used can be easily prepared by referring to the description in this publication. Further, this fluorine-based elastomer is SIFEL350
0, SIFEL3510, X-70-709, X-70
Since they are commercially available under the trade names such as -707BK and X-71-305 (manufactured by Shin-Etsu Chemical Co., Ltd.), they can also be used.

The elastic mold of the present invention can be formed of only the above-mentioned fluoroelastomer. However, natural rubber, chloroprene rubber, silicon rubber and the like generally used as the material of the elastic mold are mixed and blended. Alternatively, it may be formed. In the latter case, the compounding ratio is (fluorosilicone elastomer) / (general rubber) = 10/90 to 9
9/1 is preferred. When the amount of the fluorine-based silicone elastomer is less than 10% by weight (hereinafter abbreviated as%), oil resistance and flexibility are poor, and the effect of the present invention is impaired.

Preferred examples of blending are as follows:
10% to 90% of the fluoroelastomer of the present invention (for example, X-70-709; manufactured by Shin-Etsu Chemical Co., Ltd.) and 90 to 10%
% Silicone elastomer (RTB rubber KE1 for molding)
310ST; (manufactured by Shin-Etsu Chemical Co., Ltd.).

The molding method for forming the elastic mold of the present invention is not particularly limited, and a method generally used in injection molding, pressure molding and the like can be used.

The hardness of the elastic molding die of the present invention formed of the above-mentioned resin containing a fluorine-based elastomer is measured by using an A-type spring hardness tester specified in JIS K6301 (JIS-A). In 20-6
It is preferably in the range of 0, and particularly preferably 30 to 50. If the hardness is lower than 20, the durability is inferior and the mold deteriorates after repeated use of the mold. In addition, when a method is used in which the elastic molding die is expanded by utilizing the air pressure difference and the molded product is peeled off from the die, if the hardness is higher than 60, the elastic molding die is difficult to expand, and the gloss of the surface of the molded product is reduced. Spoil.

The hardness is measured in accordance with the JIS.
A method using a rheometer other than the standard measurement may be used. In this case, for example, in the case of an elastic molding die for lipstick having a thickness of 2.0 mm, a tooth-shaped push rod is used, and a rising speed is 6 cm / mi.
n, when measured at 15 ° C. at a depth of 3.0 mm,
A range of 350 g is preferred, and a range of 150 to 300 g is particularly preferred.

The elastic mold of the present invention thus obtained is
It is excellent in flexibility, oil resistance and durability, and can be used repeatedly and many times. Therefore, it is suitable for molding oil-based solid cosmetics represented by lipstick and bar-shaped solid powder cosmetics. Particularly, since it is a molding die produced by curing a raw material which is a fluid, an oily solid cosmetic can be molded without impairing a fine uneven pattern or surface gloss.

The elastic mold of the present invention may be transparent or opaque, but is preferably transparent to translucent in the case of an elastic mold for producing a colored article such as lipstick.
When a colored flowable molding material such as a lipstick melt (lipstick bulk) is filled, the filling state can be visually observed,
After the molded product is peeled off from the elastic molding die, it is easy to confirm the remaining state of the lipstick bulk and the like attached to the molding die. When opaque, white is preferred. Although it is impossible to visually observe the filling state, if it is white, it is easy to confirm the adhesion state of the lipstick bulk and the like in the mold after the molded article is peeled off from the elastic mold.

In order to manufacture a molded article using the molding die of the present invention, an elastic molding die is filled with a flowable molding material to be a material of the molded article, cooled, solidified, and then subjected to an elastic method. What is necessary is just to take out from a molding die. In this case, a holder can be attached to the elastic mold according to the characteristics of the molded product. For example, in the case of lipstick, if a container or inner plate is attached to the molding material injection port side of the elastic mold, without damaging the lipstick,
It is easier to remove than the elastic mold.

In the above method, the molding material can be cooled and solidified, and the obtained molded product can be taken out according to a known method. For example, air can be blown into an elastic molding die by an appropriate means, A method of expanding or a method of applying a force to the elastic mold by some means to deform the elastic mold can be used.

[0023]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples and the like.

EXAMPLE 1 Using the materials shown below, an elastic mold was formed by the following pressure molding method, and its oil expandability, hardness and color tone of the mold were evaluated and judged. Also, after attaching the container to the formed elastic mold and filling it with the heated lipstick bulk,
After cooling, the mold was removed by a method in which the elastic mold was expanded outward using a difference in air pressure (vacuum) to form a lipstick. The surface gloss of the obtained lipstick was observed, and each mold was judged. The results of these evaluations and determinations are shown in Table 1 below.

[Elastic Mold Material] Product of the Present Invention 1: Fluorine Elastomer (X-70-70)
9: Shin-Etsu Chemical Co., Ltd.) Product of the present invention 2: Fluorine-based elastomer (X-71-30)
5; Shin-Etsu Chemical Co., Ltd. Comparison 1: Silicon rubber (RTB rubber KE for molding)
1310ST; Shin-Etsu Chemical Co., Ltd.) Comparative product 2: Fluoro rubber (Daiel; manufactured by Daikin) Comparative product 3: Fluoro rubber (Afras; manufactured by Asahi Glass Co., Ltd.)

[Pressure Molding Method of Elastic Mold] A concave mold and a convex mold whose gaps have the same shape as the elastic mold are prepared when the concave mold and the convex mold are combined. After pouring the material into the concave mold, the convex mold is pressed and pressed from above. Then 20
After heating to 0 ° C., after 20 minutes, the convex mold is removed and the elastic mold is removed from the concave mold.

[Evaluation and Judgment of Elastic Molds] (A) Oil Swelling The external change dimension ratio after immersing each elastic mold in liquid paraffin for 3 hours at normal temperature was determined. Were evaluated and evaluated according to the following five levels. Those with no dimensional change are preferable without oil expansion, but those with dimensional change are not preferable because they expand with oil.

(Evaluation Criteria) Evaluation Evaluation Contents ：: Dimensional change rate is less than 0.5% ○: 〃 0.5% or more and less than 1.0% △: １ 1.0% or more, 1 Less than 2.5% ×: 〃 2.5% or more, less than 2.0% XX: 〃 3.0% or more

(A) Hardness Rheometer NRM-2002D-D (Fudo Industry Co., Ltd.)
The hardness of the elastic mold was measured under the conditions of a measurement temperature of 15 ° C., a rise rate of 6 cm / min, a depth of 3.0 mm, and use of a toothed push bar. It was judged at the stage.

(Evaluation Criteria) Evaluation Evaluation Contents: Hardness value of 150 or more and less than 250 ○: Hardness value of 250 or more and less than 350, or 100 or more and less than 150 △: Hardness value of 350 or more Less than 450 ×: Hardness value of 450 or more and less than 550 XX: Hardness value of 550 or more or less than 100

(C) Color Tone The external color of the elastic mold was observed and judged from the following three stages from transparent to colored and opaque.

(Evaluation Criteria) Evaluation Evaluation Contents ◎: Transparent to translucent ○: White to slightly colored opaque ×: Colored opaque

[Evaluation and Judgment of Lipstick Appearance] An expert evaluator evaluates the appearance of the lipstick molded using each of the above-mentioned elastic molding dies. The following five grades were used to determine the presence of peeling due to the damage.

(Evaluation Criteria) Evaluation Evaluation Contents ◎: Very glossy ○: Glossy な い: Little glossy X: Almost no gloss ×: Scratch is observed

[Results]

[Table 1]

From the results shown in Table 1, the elastic mold of the present invention was excellent in oil expandability, hardness and color tone.
Also, the lipstick filled with the elastic mold of the present invention was very glossy. From the above, it was proved that the elastic mold of the present invention has extremely good quality as a mold for lipstick.

Example 2 Fluorine-based silicone elastomer (X-70-709 (manufactured by Shin-Etsu Chemical Co., Ltd.)) having a fluorine polyether skeleton and silicon rubber (RTB rubber KE1310ST for molding)
(Manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed in the mixing ratio shown in Table 2 to form an elastic mold. The elastic mold was filled with lipstick bulk and molded, and the appearance of the resulting molded article was evaluated and judged in the same manner as in Example 1. The results are shown in Table 2.

[0038]

[Table 2]

From the results shown in Table 2, it was clarified that a glossy lipstick was obtained from the elastic mold of the present invention, which is a blend mold, and that the mold had excellent quality as a mold for lipstick.

[0040]

The elastic molding die of the present invention has both oil resistance due to the fluorine component in the material resin and flexibility due to the silicon component, and has good oil resistance and durability which do not collapse even when used repeatedly. Has the property. And since the elastic mold of the present invention has high flexibility and can be made into a free shape, if it is used, it can be used in cosmetics and soaps, foods such as chocolates and candles, etc. A product with a beautiful appearance can be obtained. In particular, it is particularly suitable for oily solid cosmetics and the like containing a large amount of oily components such as lipstick, since glossy products can be repeatedly molded for a long time. that's all

[Procedure amendment]

[Submission date] March 1, 2000 (200.3.1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction contents]

(Evaluation Criteria) Evaluation Evaluation Contents: Dimensional change rate is less than 0.5% ○: 〃 0.5% or more and less than 1.0% △: １ 1.0% or more, 1 Less than 0.5% ×: 〃 1.5 % or more, less than 2.0% XX: 〃 2.0 % or more

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // A61K 7/02 A61K 7/02 T C08J 5/00 CFG C08J 5/00 CFG F-term (Reference) 4C083 CC13 DD21 FF06 4F071 AA54 AA68 AH19 BB01 BB03 BB12 BC07 4F202 AJ03 AJ11 AM32 CA01 CB01 4J002 CL001 EX036 FD146 GB00 4J035 BA02 CA021 CA141 CA16M CA16U CA161 CA19N CA191 EA01 EB01 GB03 FB03 GB03 FB03 FB03 GB03 FB03

Claims (7)

[Claims]
1. 1. A fluorine-containing amide compound represented by the following formulas (A), (B) and (A): [Wherein R ¹ and R ² are monovalent hydrocarbon groups, Q is the following formula (2) or (3): (Here, R ³ represents a divalent hydrocarbon group which may have one or more oxygen, nitrogen or silicon atoms in the bond) or (Where R ⁴ and R ^{5 each} represent a divalent hydrocarbon group), Rf represents a divalent perfluoroalkylene group or the like, and a represents an integer of 0 or more.) (B) One molecule Having one or more monovalent perfluorooxyalkyl groups, monovalent perfluoroalkyl groups, divalent perfluorooxyalkylene groups or divalent perfluoroalkylene groups, and having two or more hydrosilyl groups An elastic mold formed of a resin containing a fluorine-based elastomer obtained by polymerizing a fluorine-containing organohydrogensiloxane.
2. 2. A fluorine-containing amide compound represented by the following formulas (A), (B) and (A): [Wherein, R ¹ and R ² are monovalent hydrocarbon groups, Q is the following formula (2) or (3): (Where R ³ represents a divalent hydrocarbon group which may have one or more oxygen, nitrogen or silicon atoms interposed in the bond) or (Where R ⁴ and R ^{5 each} represent a divalent hydrocarbon group), Rf represents a divalent perfluoroalkylene group or the like, and a represents an integer of 0 or more.) (B) One molecule Having one or more monovalent perfluorooxyalkyl groups, monovalent perfluoroalkyl groups, divalent perfluorooxyalkylene groups or divalent perfluoroalkylene groups, and having two or more hydrosilyl groups A composition containing a fluorine-containing organohydrogensiloxane, wherein the amount of (B) is 0.5 to 5 mol as a hydrosilyl (Si-H) group per 1 mol of an aliphatic unsaturated group in the composition. An elastic mold formed of a resin containing a fluoroelastomer obtained by curing a composition having an amount of:
3. 3. The hardness (JIS-A) after formation is 2
   The elastic mold according to claim 1, wherein the elastic mold is in a range of 0-60.
4. 4. The elastic mold according to claim 1, which is used for molding an oily solid cosmetic.
5. 5. A molded product, characterized in that a fluid molding material is filled in the elastic molding die according to any one of claims 1 to 4, which is cooled, solidified, and taken out of the elastic molding die. Manufacturing method.
6. 6. The method for producing a molded article according to claim 5, wherein the molded article is a solid cosmetic containing an oily component.
7. 7. The flowable molding material is lipstick bulk,
   The method for producing a molded product according to claim 5, wherein the molded product is a lipstick.