JPH02202553A - Molded article of synthetic resin composition having excellent releasability and water repellency - Google Patents

Abstract

PURPOSE:To obtain molded articles of synthetic resin having improved mold release characteristics in molding, releasability, water repellency, stain resistance, lubricating properties, etc., by adding a specific silicone compound to a molding thermoplastic synthetic resin. CONSTITUTION:A thermoplastic resin (e.g. polyolefin-based resin, polyester-based resin or acrylic resin) is blended with (A) a modified silicone compound prepared by reacting A1: a silicone compound (e.g. polymethylhydrogen siloxane) containing one or more hydrogens with A2: a hydrocarbon compound (e.g. alpha- olefin) containing one or more double bonds to be reacted with H of A1 and (B) one or more selected from modified silicone compounds prepared by reacting B1: a polyolefin-based resin (e.g. ethylene acrylic acid copolymer) containing a functional group on the side chain with B2: a silicone compound (e.g. epoxy modified dimethylpolysiloxane) containing a functional group to be reacted with the functional group of B1 to give films, sheets or three-dimensional structures.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic synthetic resin molded article with improved surface properties and moldability during molding. More specifically, using a modified silicone compound that can be unevenly distributed in the surface layer, ? This invention relates to a thermoplastic synthetic resin molded product that has improved release properties, (θ water resistance, lubricity, etc.), and at the same time improved moldability during molding.

[Conventional technology and problems]

In a molding method using a mold such as injection molding, a mold release agent is internally added to the resin of the molded product in order to improve release from the mold during molding. Additionally, silicone resin composition additives are used for the purpose of imparting and improving surface lubricity and wear resistance to molded products.

Furthermore, surface properties are imparted to films, sheets, and fibers by post-treatments such as coating with silicone compounds after molding or secondary processing.

However, although the mold release agent added internally to the molded product resin achieves the purpose of improving mold release from the mold, bleed-out of the mold release agent to the surface of the molded product is still observed, and the product reduce value; The internal addition of silicone resin composition additives to molded products is mainly aimed at improving the sliding properties and abrasion resistance of plastic parts, but the effect of imparting releasability and aqueous properties is small.

When a film, sheet, or fiber is subjected to surface treatment after molding or secondary processing, not only the number of surface treatment steps increases, but the durability of the effect is not sufficient.

Furthermore, for example, silicone processing requires curing, and especially for fibers, there are restrictions on processing conditions to avoid deterioration of physical properties, making processing complicated.

[Means for solving problems]

The present invention aims to solve the above problems, and by adding a specific silicone compound to a thermoplastic synthetic resin for molding, it not only improves mold releasability during molding, but also improves the release properties after molding. The present invention was completed by discovering that it is possible to impart and improve releasability, 1B aqueous properties, and even lubricity to molded products without the need for processing, and that these effects last for a long time. This is what I did.

That is, the present invention provides a synthetic resin with excellent mold releasability and (8) aqueous properties, characterized by comprising a thermoplastic resin and at least one silicone compound selected from the following silicone compounds (A) and (B). Molding.

(8) A modified silicone compound obtained by reacting a silicone compound having at least one hydrogen group with a hydrocarbon compound having at least one double bond that reacts with the hydrogen group.

(B) A modified silicone compound obtained by reacting a polyolefin resin having a functional group in its side chain with a silicone compound having a functional group capable of reacting with the functional group of the polyolefin resin.

The content is as follows.

The modified silicone compound used in the present invention includes (A) a silicone compound having at least one hydrogen group and a double bond that reacts with the hydrogen group, as described in JP-A-63-3076. Modified silicone compounds obtained by reacting with at least one hydrocarbon compound, and
B) A modified silicone compound obtained by reacting a polyolefin resin having a functional group in its side chain with a silicone compound having a functional group that can react with the functional group of the polyolefin resin is preferred, and these compounds may be used alone or in combination. It is used as

In the modified silicone compound (A), examples of the silicone compound having at least one hydrogen group include polymethylhydrodienesiloxane, polymethylhydro-dimethylsiloxane copolymer, and the like. As a hydrocarbon compound having at least one double bond, α-
Examples thereof include olefin, polyethylene wax, 4-polybutadiene, 1,2-polybutadiene, polybutene, 1-octadecene, and mixtures thereof.

In the modified silicone compound (B), examples of the polyolefin resin having a functional group in the side chain include ethylene/acrylic acid copolymer resin, ethylene/methacrylic acid copolymer resin, and ethylene/vinyl urethane.

Examples include alcohol copolymer resins, modified polyolefin resins in which a functional group such as maleic acid or maleic anhydride is introduced into polyethylene or propylene. Examples of silicone compounds having a functional group that can react with the functional group of the polyolefin resin include carboxyl-modified dimethylpolysiloxane, epoxy-modified dimethylpolysiloxane, isocyanate-modified dimethylpolysiloxane, amino-modified dimethylpolysiloxane, and alcohol-modified dimethylpolysiloxane. Examples include modified silicone compounds into which functional groups such as dimethylpolysiloxane are introduced.

The molded article in the present invention is not particularly limited, and includes fibers,
All molded products obtained by known molding methods, such as films, sheets, and three-dimensional structures, are included.

When the molded product is a fiber, examples of the resin for the fiber include polyethylene, polypropylene, polyethylene terephthalate, etc., and by adding a modified silicone compound, it is possible to impart or obtain a fiber with improved peelability and IB water resistance. . The amount added depends on the silicone content of the modified silicone compound and the application, but for example, silicone content of 4
0 to 60%, 0.5 to 8 wtχ, more preferably 1 to 4
The addition of wtχ imparts releasability and (θ aqueous property.0.
If it is less than 5wtX, the effect will not be sufficient, and if it exceeds 3wtχ, the number of yarn breakages during spinning will increase. When the fibers obtained in this way are processed into a fabric and used as a base material for a cloth adhesive tape, for example, the adhesive tape does not need to be subjected to a peeling process on the back side. As the fiber, polyethylene, polypropylene, polyethylene terephthalate, etc. are used for both the warp yarn and the weft yarn, but a co-modified silicone compound may be added to the warp yarn and the weft yarn, or it may be added to only one of them. .

The peeling force is controlled by increasing or decreasing the amount of the modified silicone compound added, but it is also controlled by whether or not the modified silicone compound is added to the warp and weft threads used. It may be interwoven in order to impart properties such as hand tearability, which are required physical properties for cloth adhesive tapes. Additionally, additives such as colorants can be mixed at the same time, if necessary.

Fabrics woven with modified silicone compound-added fibers have a high fJl water and waterproof function, and are therefore suitable for applications that require waterproofing, such as umbrellas, cloth sheets, and tents. In addition, polyolefin resins are used for fishing nets and ropes due to their specific gravity, strength, price, etc., but when these items are pulled out of the water, water gets between the fibers and water is brought in, which increases the weight. There are increasing drawbacks. However, since the modified silicone compound-added fiber of the present invention has high TA water performance, it solves this problem and is suitable for use in fishing nets, ropes, etc.

Furthermore, gauze used for medical purposes requires a liquid-absorbing action, but on the other hand, it tends to stick to the wound and cause re-injury when the gauze is replaced. In this case, apply directly to the wound area.
This problem can be solved by using fibers of polyethylene or polyethylene terephthalate resin added with the modified silicone compound of the present invention for the IN of the contacting gauze, or by using a gauze obtained by interweaving these with cotton. Can be done.

As mentioned above, the control of fiber release properties and 10 aqueous properties can be controlled by increasing or decreasing the amount of modified silicone compound, the physical properties of the rolls (roll material, roll surface irregularities, roll temperature, etc.), stretching This is also possible depending on the presence or absence of treatment, heat treatment after processing, etc. This is because uneven distribution and bleeding of the modified silicone compound added to the fiber resin onto the surface is controlled.

When the molded product is a film or sheet, examples of molding resins include low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, polyethylene terephthalate, polybutylene lenticulate resin, polymethylmethacrylate resin, etc. . The film or sheet can be obtained by extrusion molding such as T-die extrusion or inflation. In this case as well, it depends on the silicone content of the modified silicone compound relative to the molding resin, but for example, when the silicone content is 40 to 60%, if releasability is particularly required, 0.5 to 15 wtX, more preferably 1 ~6wtχ is added. If it is less than 0.5 wtχ, the effect is not sufficient, and if it exceeds 15 wtχ, extrusion becomes difficult.

The obtained film or sheet can be used as a base material for adhesive tapes, as well as a separator for envelopes with sealing glue, as well as woven fabrics.
It is suitable for use as a separator for emergency adhesive wounds, and furthermore, a separator for medical skin patches. In particular, polyethylene terephthalate is suitable for the skin-patch medicinal separator in terms of film strength and function as a barrier layer for drugs.

Films and sheets can be made into adhesive tapes by immediately applying adhesive processing without the need for backside peeling processing.
It can be processed into split cloth or split yarn, and then woven into cross yarns to be used as an adhesive tape base material (cross yarn adhesive tape). In this case, as in the case of cloth adhesive tapes using fibers, the releasability can be controlled by the processing method of the cross yarn and the presence or absence of interweaving. It is also possible to use additives such as colorants. Like other molded products, the film or sheet is also provided with not only releasability but also water repellency and lubricity. Taking advantage of these properties, it is also useful for applications such as curing sheets for construction and snow prevention sheets used in multilingual regions.

When forming a film or sheet, the same level of releasability and fJi water resistance can be imparted to both sides of the film.

However, by selecting the surface properties and materials of the substance that comes into contact with the film or sheet surface during molding, both sides of the film sheet can have different levels of releasability and IC water-based (IC)
Differential peeling and different tΩ water) can be applied. For example, when a film or sheet is formed using process paper, the peelability of the surface of the film or sheet in contact with that surface depends on the physical properties (cloak skin/mirror skin) and polarity of the surface of the process paper used. 18 Since the aqueous property changes, it is possible to control the peelability and IC aqueous property by selecting the processing paper, and it is possible to obtain an asymmetric film or sheet.

As mentioned above, the control of the peelability and water repellency of a film or sheet is similar to the molding of fibers, and the addition or decrease of the amount of modified silicone compound is a matter of heat, the material of the cooling roll during molding, the surface unevenness, and the surface polarity. This is possible depending on the roll temperature, etc., and also on the polarity and shape of the material in contact with the surface during molding, the presence or absence of stretching treatment, heat treatment after processing, etc.

When the molded article is a three-dimensional structure, examples of the molding resin include low-density polyethylene, high-density polyethylene, mixed resins thereof, polypropylene, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, and the like. Molding is performed by injection molding, blow molding, etc.

In this case, it is mainly used for the purpose of imparting and improving the IC aqueous properties of the molded product, as well as imparting and improving its releasability from the mold, and the modified silicone compound is added from 0.5 to 1 liter.
Qwtχ, preferably 1 to 6-[χ, achieves that objective. If it is less than 0.5wtχ, the effect is not sufficient, and if it is less than 10w
Although it is possible to apply an additional force of 11 beyond t'1, no greater water repellency can be expected.

For example, containers for storing foods and the like are desired to have good drainage after washing, and the modified silicone compound of the present invention is particularly suitable for this purpose because it has excellent T8 aqueous properties. Furthermore, stain resistance is also imparted. It is also suitable as a bottle, particularly as a container for aqueous emulsion liquids or dispersion liquids (adhesives, paints), etc.

Polymethyl acrylate has high transparency and is used as a substitute for the front glass of headlights, but by adding a modified silicone compound, it can prevent raindrops from adhering to it and at the same time provide antifouling properties.

Furthermore, by imparting IC water-based properties and peelability, it can also be used as formwork panels for concrete.

Furthermore, in injection molding and blow molding that use molds, it is important for the molded product to release smoothly from the mold, but modified silicone compounds do not provide mold release properties. , improve processability.

Molded products! 8 water-based and! -11 Control of detachment is
It is a matter of heat theory that the amount of modified silicone compound added can be increased or decreased, and the temperature of the mold during molding can also be changed.
Furthermore, it is also controlled by the surface and material (shape and polarity) of the mold.

As mentioned above, the addition of inorganic/organic fillers and colorants to fibers, films, and sheet three-dimensional structures to which modified silicone compounds have been added is a hot topic, and commonly used additives,
For example, antioxidants, ultraviolet absorbers, flame retardants, antistatic agents, etc. are used as necessary. By adding inorganic/organic fillers, it is possible to impart reinforcing effects, shielding effects, lubricity effects, antistatic effects, etc., and also control peelability and IC water resistance.

[Action/Effect]

The modified silicone compound used in the present invention is generally 26
Decomposition begins at temperatures between 0 and 280°C.

Therefore, for example, when a modified silicone compound is added to a Heath resin and the resin is extruded and laminated onto a paper base material, etc., the resin temperature is extruded at around 300° C., so a considerable drop in performance is unavoidable. However, when processing a single molded product, the resin temperature is generally up to 260°C, so
The advantage is that there is no need to worry about disassembly, and its performance can be fully demonstrated.

The modified silicone compound is added to the resin of the molded product, and is unevenly distributed and bleed onto the surface of the molded product, creating a state similar to that of a silicone coating on the surface of the molded product, and extremely effectively reducing peelability and aqueous properties. manifest. In particular, the modified silicone compound of the present invention reduces the adhesion force of water droplets to the surface by reducing the difference between the advancing contact angle and the receding contact angle of 20 @ or less in the contact angle between the surface of the modified silicone compound-added molded article and water. It has the effect of Due to this action, the altitude is 1
8 Aqueous properties are imparted.

Products with silicone compounds as the main chain and hydrocarbons added to the grafting technique are compatible with base resins such as polyolefin resins, and exhibit a so-called anchor effect as if they had grown roots in the base resin. . (As a result, the main chain of the silicone compound becomes firmly fixed on the surface of the base resin, effectively and inexpensively exhibits releasability and 1a aqueous properties, and furthermore, molded products with virtually no bleed at room temperature. give.

On the other hand, modified silicone compounds with polyolefin resin as the main chain have good compatibility with polyolefin resin,
The silicone chains integrated with the base resin and grafted become firmly fixed on the base resin surface, effectively and stably exhibiting peelability and water repellency, and can be molded with virtually no bleed at room temperature. provide products.

〔Example〕

The present invention will be explained below with reference to Examples and Comparative Examples.
Of course, the present invention is not limited to these. still,
In the following, unless otherwise specified, parts by weight and % by weight are respectively meant. Moreover, the measurement was performed at 23° C. and 65% RH.

Synthesis Example 1 Polymethylhydrodienesiloxane (P-300, M
W=22000) 45.6 parts, α-olefin (
"Diaren-30", Mitsubishi Chemical Industries type, MW=650
), 8 parts of 0.1% H, PtC1, .6H1O tetrahydrofuran solution were charged into a reactor, and the
The addition reaction was carried out for a period of time, and the reaction was further carried out at 130°C for 18 hours.

The reaction was stopped when the viscosity of the reaction product reached approximately 10,000 cps. The reaction product was washed three times with acetone to remove unreacted parts, and purified and dried. The silicone content of the release agent obtained was 45.6%.

Synthesis Example 2 Ethylene/acrylic acid copolymer resin [manufactured by Dow Chemical Japan ■, Primacol-3440160 parts and one end epoxy-modified dimethylpolysiloxane (h=lO000) 4
0 part was charged into a reactor and subjected to an addition reaction at 150°C for 5 hours. After the reaction was completed, it was confirmed at G, P, and C that there was no unreacted soricone.

The reaction product was purified by dissolving it in xylene and reprecipitating it with n-hexane. The silicone content was 40%.

Example 1 (Example in case the molded product is a fiber) The modified silicone compound obtained in Synthesis Example 1 was added to high-density polyethylene "HIZESOX 2200J, I (Mikata Petrochemical Co., Ltd., former -5,5, d=0 .968) to produce a spinning resin using a pelletizer at a die temperature of 180°C.

6 melt spinning was performed using the above spinning resin at a die temperature of 180°C, and the single yarn fineness was 7 denier (strength 6.1 g/d).
, elongation of 32%) and a total fineness of 84 denier. This is used as a warp yarn, and the weft yarn is made of the same resin as the warp yarn, with a single yarn fineness of 5 denier (strength 5.6
g / d, elongation 50%), using polyethylene filament with a total fineness of 80 denier, vertical filament driving density 39 wood/in / horizontal filament driving density 4
A plain weave polyethylene woven fabric consisting of 4 wood/in was obtained.

One side of the obtained plain-woven polyethylene fabric was coated with low-density polyethylene "Mirason 16spJ (Mikata Petrochemical Co., Ltd., formerly -4,
5, d=0.923) was extruded and laminated at a die temperature of 300°C to provide a 45 μm laminate layer. Furthermore, on the laminate layer, 70μ of the rubber thread adhesive “Olivine BPS-2411J (manufactured by Toyo Ink) was applied using a conventional method.
The adhesive tape was coated (wet), dried at 70° C. for 3 minutes, and rolled into a roll (11) to obtain an adhesive tape, and its performance was evaluated. The results are shown in Table 1.

Comparative Example 1 An adhesive tape was obtained in the same manner as in Example 1, except that only the high-density polyethylene "HIZEX 2200 JJ" used in Example 1 was used, and its performance was evaluated. The results are shown in Table 1. .

Rewinding property The force required when an adhesive tape stored at 70° C. and 65% RH for 48 hours was unwound at a speed of 30 m/min was measured.

Nail adhesion property: The adhesive tape was stored at 70°C in a 165% R1+ atmosphere for 48 hours, and the adhesive tape was pressed back and forth at a speed of 51 for 1 second to the cloth base side of the adhesive tape with a 4° 5kg rubber roller, and the adhesive tape was 0.3 m long.
The resistance force is measured when the adhesive tapes are peeled off in a 180° direction at a speed of 180°.

Migration properties of modified silicone compound (residual adhesion rate) (%) A standard adhesive tape was attached to the cloth base side of the adhesive tape stored for 48 hours at 70°C in a 65% R1+ atmosphere in the same manner as measured in Example 2. Then, the residual adhesion rate of the adhesive tape after peeling was calculated.

Example 2 (Example when the molded product is a film) The modified silicone compound obtained in Synthesis Example 2 was processed into low density polyethylene “Mirason 16pJ (Mikata Petrochemical Co., Ltd., formerly ==
3%, d=0.923), and a film resin was produced using a pelletizer at a die temperature of 180°C.

The film resin is produced using a T-die extruder at a die temperature of 240.
℃ and extruded onto polyethylene terephthalate film as process paper. The thickness of the obtained film was 40 μm
Met. Evaluation of the peelability of the obtained film is shown in Table 2. Mirror finish press roll touch surface and polyethylene terephthalate film touch surface! 1.Films with different release properties were obtained.

Comparative Example 2 Low-density polyethylene “Mirason 16” used in Example 2
Extrusion was carried out in the same manner as in Example 2 except that only “p” was used,
The peelability of the mirror-finished press roll touch surface of the film and the polyethylene terephthalate film touch surface was measured. The results are shown in Table 2.

Table 1: Residual adhesion rate *Residual adhesion rate: Peeling force
"Elm Tape" (manufactured by Soken Kako) width 25 x length 21
It was adjusted to 0 tuna and bonded together by applying pressure once back and forth at a speed of 51 TA for 1 second using a rubber roller weighing 4.5 kg.

After applying the tape, load 20g/cffl, 70℃, 65%
The sample was aged in an RH atmosphere for 20 hours and measured after being allowed to cool. Fang, (l release force is 0.3 using an autograph tensile tester.
Measurements were made at a peel angle of 180'' at a speed of m/min.

Example 3 (Example in case the molded product is an injection molded product) The modified silicone compound obtained in Synthesis Example 1 was processed into low density polyethylene "Mirason 403pJ (manufactured by Mikata Petrochemical Co., Ltd., formerly =
7.0, d=0.920) in an amount of 5%, and a molding resin was produced using a pelletizer at a die temperature of 180°C.

Using molding resin, cylinder temperature 230℃, injection pressure 8
00kg/cd, mold temperature 40℃, vertical x horizontal x
A food container with a height (10 x 15 x 5 cm+) was molded. The obtained molded product had high 1a aqueous properties and good drainage properties. The results are shown in Table 3.

Comparative Example 3 Low density polyethylene “Mirason 40” used in Example 3
A molded product was obtained in the same manner as in Example 3, except that only 3pJ was used, and the water repellency and drainage properties were evaluated. The results are shown in Table 3.

3. Drainability After soaking the molded product in water, take it out and lightly drain it once.
(shake the molded product by hand) and measure the weight increase rate of the molded product after water immersion/FI.

The contact angle between the surface of the 1B aqueous molded product and water was measured. The measurement was carried out using a contact angle measuring device according to the Kobe University method described in "Kobunshi" Vol. 33, August issue, page 639 (1984).

θa; advancing contact angle θ”: Receding contact angle Δθ=θa−θ

Claims (1)

[Claims] 1. Synthesis with excellent mold releasability and water repellency, characterized by comprising a thermoplastic resin and at least one selected from the following silicone compounds (A) and (B). Resin molded product. (A) A modified silicone compound obtained by reacting a silicone compound having at least one hydrogen group with a hydrocarbon compound having at least one double bond that reacts with the hydrogen group. (B) A modified silicone compound obtained by reacting a polyolefin resin having a functional group in its side chain with a silicone compound having a functional group capable of reacting with the functional group of the polyolefin resin. 2. The molded article according to claim 1, wherein the thermoplastic resin is a polyolefin resin. 3.Claim 1, wherein the thermoplastic resin is a polyester resin.
The molded product described. 4. The molded article according to claim 1, wherein the thermoplastic resin is an acrylic resin. 5. The molded article according to claim 1, wherein the molded article is a fiber. 6. The molded article according to claim 1, wherein the molded article is a film or a sheet. 7. The molded article according to claim 1, wherein the molded article is a three-dimensional structure.