JPH04146906A - Improver for processability, water repellency and oil repellency of thermoplastic resin and thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the title improver excellent in the function of improving the processability of a thermoplastic resin and the staining resistance, etc., of a molding by using a fluoroacrylic polymer comprising fluoroalkyl (meth) acrylate units and having a reduced viscosity above a specified value. CONSTITUTION:A fluoroacrylic polymer at least partially consisting of at least one kind of structural units selected among fluoroalkyl acrylate and fluoroalkyl methacrylate units (e.g. 2,2-difluoroethyl methacrylate or 2,2,3,3-tetrafluoropropyl methacrylate) and having a reduced viscosity of 2 or above as measured at 25 deg.C in a solution prepared by dissolving 0.1g of the polymer in 100ml of chloroform is produced. This polymer is used as an improver for the processability, water repellency and oil repellency of a thermoplastic resin (e.g. vinyl chloride resin).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is to improve the processability of a thermoplastic resin by blending it into a thermoplastic resin, and to impart stain resistance, water repellency, and oil repellency to molded products thereof. The present invention relates to a fluorinated acrylic polymer that can be used as a fluorinated acrylic polymer, and further relates to a thermoplastic resin composition obtained by blending the fluorinated acrylic polymer with a thermoplastic resin.

(Prior Art) Thermoplastic resins, especially vinyl chloride resins, are widely used in various fields due to their excellent physical and chemical properties.However, vinyl chloride resins have various advantages. It has the disadvantage of poor workability. As a way to overcome this drawback, adding processing aids and lubricants such as plasticizers and copolymers mainly composed of methyl methacrylate has been carried out, but this is not a general solution. There wasn't. In order to solve these problems, various research and development efforts have been carried out, and as a result, the
Publication No. 781, Special Publication No. 52-3668, Special Publication No. 5
Vinyl chloride resin compositions have been proposed as disclosed in Japanese Patent No. 3-2898 and the like.

(Problems to be Solved by the Invention) The above-mentioned compositions that have been proposed so far are intended to maintain various good physical and chemical properties of vinyl chloride resin even after molding. , some results have been obtained.

However, even if the above-mentioned auxiliary agents are added and blended, the processing temperature of vinyl chloride resin is close to the thermal decomposition temperature, the molding area is narrow, and the molding workability is extremely poor, so special processing machines are required. However, there was a problem in that it was not possible to obtain expected physical properties without using special techniques.

On the other hand, there is a need for processing aids that can be used to form resin compositions that allow molded products to have good stain resistance, water repellency, oil repellency, gloss, and transparency. There has been no composition that fully satisfies the demands of the market.

In order to solve the above problems, as a result of intensive studies, it was discovered that a fluorinated acrylic polymer having fluorinated alkyl acrylate units or fluorinated alkyl methacrylate units with a reduced viscosity of 2 or more can solve these problems. By blending a specific amount of this fluorinated acrylic polymer with other thermoplastic resins, the processability of the thermoplastic resins is improved, and the molded products are further improved in stain resistance, water repellency, and repellency. It was discovered that oiliness can be imparted, and the present invention was achieved.

(Means for Solving the Problems) That is, the first invention of the present invention contains at least one type of fluorinated alkyl acrylate unit and fluorinated alkyl methacrylate unit as all or a part of a polymer constitutional unit, and The viscosity ηSp/c (0.1 g of polymer dissolved in 100-chloroform and measured at 25°C) is 2
．． This is an agent for improving the processability and water and oil repellency of a thermoplastic resin made of a fluorinated acrylic polymer having a molecular weight of 0 or more.

Further, the second invention of the present invention provides a reduced viscosity in which all or a part of the polymer constituent units contain at least one type of fluorinated alkyl acrylate units and fluorinated alkyl methacrylate units in an amount of 7 per 100 parts by weight of the thermoplastic resin. ηs
Thermoplastic resin containing 0.1 to 20 parts by weight of a fluorinated acrylic polymer with p/c (0.1 g of polymer dissolved in 100-chloroform L and measured at 25°C) of 2.0 or more It is a composition.

First, the fluorinated acrylic polymer in the present invention will be explained.

In the present invention, fluorinated alkyl acrylates and fluorinated alkyl methacrylates have a basic structural formula, where m: an integer of 1 to 5, n: an integer of 1 to 10, X: F or H 7:H or CH3. Those that can be used are used.

Among these, fluorinated alkyl methacrylates include 2,2-difluoroethyl methacrylate (2FM) and 2,2,2-trifluoroethyl methacrylate (3F).
M) 2,2,3,3-Tetrafluoroprobil Mec 1
Root (4FM) 2.2,3,3.3-pentafluoropropyl methacrylate (5FM) 2.2+3+314
14-hexafluorobutyl methacrylate (6FM)
etc.

In addition, as the fluorinated alkyl acrylate, 2.2.2-trifluoroethyl acrylate (3FA
) etc.

These can be used alone or in combination of two or more.

In the fluorinated acrylic polymer according to the present invention, all or part of the constituent units thereof are composed of at least one of a fluorinated alkyl acrylate unit and a fluorinated alkyl methacrylate unit.

The fluorinated acrylic polymer in the present invention preferably contains at least 5.0% by weight of at least one of fluorinated alkyl agellylate units and fluorinated alkyl methacrylate units as a constitutional unit. preferable.

The fluorinated acrylic polymer in the present invention may be composed of
The monomer copolymerizable with fluorinated alkyl acrylate and fluorinated alkyl methacrylate is not particularly limited, and any appropriate monomer may be used depending on the final purpose. Examples of the copolymerizable monomers include (meth)acrylates such as methyl methacrylate, ethyl acrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, ethyl agellylate, propyl acrylate, Examples include butyl acrylate, 2-ethylhexyl acrylate, pencil acrylate, acrylamide, acrylic acid, methacrylic acid, styrene, alkyl-substituted styrene, halogenated styrene, acrylonitrile, methacrylonitrile, and the like. These can be used alone or in combination of two or more.

The fluorinated acrylic polymer of the present invention may be any polymer such as a random copolymer, a polymer produced by a two-stage polymerization method, or a multistage polymer such as a polymer produced by a three-stage polymerization method. Specifically, the monomer composition and polymerization order of the fluorinated acrylic polymer of the present invention are (a) MMA=St/BA''MM
A/FM and/or FA.

(b) MMA 4-5t/BA/FM and/or F
A-MMA (C) MMA←FM and/or FA/B
A=MMA(d) M←BMA/BA-MMA/F
M and/or FA (e) MMA/FM and/or F
A-St/BA-MMA(f) FM and/or FA 4-5t/BA-MiJ+A(g)
MMA = FM and/or FA←MMA(h) M
MA←St/BA 1~FM and/or FA(i)
F and/or FA-FM and/or FA-1 member A (j
) FM and/or FA-FM and/or EA4-F
Vl and/or FA k) HMA/FM and/or FA=M feathers 1,)
FM and/or FA-MMAm) MMA 4-MM
A/FM and/or FAn) MMA-FM and/or FA o) FM and/or FA-FM and/or FA (p
) FM and/or FA/EA-Bar A(q) MM
A 4-FM and/or FA/EA (but MMA
: Methyl methacrylate, S: Styrene, BA:
Butyl acrylate, EA: Ethyl acrylate,
BMA: butyl methacrylate, FM: fluorinated alkyl metal rylate, FA: fluorinated alkyl acrylate. ) etc.

The fluorinated acrylic polymer of the present invention has an excellent processability improvement effect on thermoplastic resins and good secondary processability, such as slowing down the melting rate during molding, and large drawdown during molding, making it easy to mold large-sized molds and bottles. In order to obtain good viscosity, the reduced viscosity of the entire polymer needs to be 2.0 or more. Furthermore, if the Tg of the polymer is 90° C. or higher, the resin will not melt during extrusion molding and unmelted materials will likely occur, which is not preferable.

The reduced viscosity can be adjusted as appropriate by adjusting the chain transfer agent, catalyst, and polymerization temperature used during polymerization. Further, the reduced viscosity ηsp/c defined in the present invention is measured by dissolving 0.1 g of the above fluorinated acrylic polymer in 100 d of chloroform and measuring at 25° C. using an Ostwald viscometer.

In the case of a random copolymer, the reduced viscosity of the entire polymer is 2.0 or more, and the higher the viscosity, the better. °The temperature is 90℃
In the case of polymers obtained by the 62-stage polymerization method, the following are preferred, the reduced viscosity of the individual polymers in the first or second stage is irrelevant, and the reduction of the final polymer obtained in the two-stage polymerization method is It is sufficient that the viscosity is 2.0 or more, and it is preferable that the Tg is 90° C. or less. In the case of polymers obtained by the three-stage polymerization method, the reduced viscosity of the individual polymers in the first, second, or third stages is irrelevant, and the reduced viscosity of the final polymer obtained by the three-stage polymerization method is , 2.0 or more, and preferably has a Tg of 90° C. or less.

The reduced viscosity of the polymer is 2.0 or less, and the Tg is 90'C.
In the above case, during extrusion molding, the resin is not melted during molding and unmelted materials are likely to be generated, which is not preferable.

When methyl methacrylate is used as a polymer constituting the second stage polymer in the two-stage polymerization method or the third stage polymer in the three-stage polymerization method, the amount of methyl methacrylate is It is sufficient as long as it is a dominant amount of the monomer.

In addition, if an acrylic ester or fluorinated acrylic monomer is used as the material, the second or third stage
The amount is preferably 10 parts by weight or less based on 100 parts by weight of Kaneko Zimmer in the step. If it is more than 10 parts by weight, the resulting fluorinated acrylic polymer will have poor compatibility with vinyl chloride resin and will block latex agglomeration. It is difficult to form a complete powder, and poor dispersion occurs during molding, which is undesirable.

Polymerization methods for producing the fluorinated acrylic polymer of the present invention include, for example, emulsion polymerization, suspension polymerization, bulk polymerization, etc. Among these, application of emulsion polymerization is preferred. In order to apply this emulsion polymerization method and form a fluorinated acrylic polymer with a two-layer or three-layer structure, it is necessary to proceed with the polymerization without adding any emulsifier during the second and third stages of polymerization. ,2
It is desirable to substantially suppress the formation of homopolymers of the monomer components constituting the stage and third stage.

As the emulsifier, any known emulsifier may be used, such as ordinary anionic, cationic or nonionic surfactants, and fluorine-based emulsifiers. Depending on the type of emulsifier used, if the polymerized PI (PI) is on the alkaline side, an appropriate pH adjuster may be used to prevent hydrolysis of the acrylic ester. Boric acid - potassium chloride - sodium hydroxide, potassium dihydrogen phosphate - disodium hydrogen phosphate, boric acid - potassium chloride - sodium carbonate, boric acid - sodium carbonate, potassium hydrogen citrate - citric acid, potassium dihydrogen phosphate - boron Sand, disodium hydrogen phosphate-citric acid, etc. can be used.

In addition, as a polymerization initiator, water-soluble, oil-soluble single system,
For example, a water-soluble inorganic initiator such as a normal persulfate may be used alone, or a redox initiator may be used in combination with a sulfite, bisulfite, thiosulfate, etc. Both can be used as . Further examples include redox initiators such as organic hydroperoxide-sodium formaldehyde sulfoxylate, azo compounds, and the like.

The fluorinated acrylic polymers explained above include vinyl chloride resin, polycarbonate resin, polyester resin, ABS
resin, styrene resin, MBS resin, methacrylic resin,
Per 100 parts by weight of thermoplastic resin such as polyethylene resin,
By blending 0.01 to 2.0 parts by weight, it is possible to give the thermoplastic resin an excellent processability improvement effect and good secondary processability. Moreover, the molded product has excellent stain resistance,
Becomes water repellent and oil repellent.

The amount of fluorinated acrylic polymer added to the thermoplastic resin is 2.
If the amount exceeds 0 parts by weight, the molten resin will thicken during molding, resulting in poor moldability; If it is less than O1, the improvement in workability and secondary workability will be small and the moldability will be poor, which is not preferable. The fluorinated acrylic polymer of the present invention may be added to a thermoplastic resin by mixing according to a conventional method.

The resin composition may contain organic tin compounds, lead-based, barium-based, zinc-based metal soaps, stabilizers such as epoxy processed products, stearic acid, etc. as necessary.
Filling with lubricants such as ester wax, paraffin wax, stearyl alcohol, phthalate esters, phosphate esters, fatty acid esters, plasticizers such as epoxy, colorants such as carbon black and titanium oxide, calcium carbonate, asbestos, etc. In addition, a blowing agent such as ammonia carbonate or sodium bicarbonate as an inorganic blowing agent, and a nitro blowing agent, a sulfohydrazide blowing agent, an azo blowing agent, etc. as an organic blowing agent may be blended.

Hereinafter, the present invention will be explained in further detail with reference to Examples and Comparative Examples. In addition, all "parts" in Examples and Comparative Examples indicate parts by weight.

In addition, the reduced viscosity ηsp/c of each polymer is the ηsp/c value when polymerized with each monomer composition. ηsp/c is determined by polymerizing with a specified emulsifier, polymerization initiator, and polymerization temperature, and chain transfer. The reduced viscosity ηsp/c was measured using the agent as a variable, and η
It was set as sp/c.

Next, methods for evaluating each characteristic in Examples and Comparative Examples will be described.

(Properties of thermoplastic resin composition) 3 parts of each polymer obtained in Examples 1 to 35 and Comparative Examples 1 to 8 was added to polyvinyl chloride resin (average degree of polymerization 700) 10
0 parts of butyltin mercaptide, 1.0 parts of epoxy auxiliary agent, and 0.5 parts of dibutyltin malate in a Henschel mixer to produce inventive examples (1 to 35) and comparative examples (2- A vinyl chloride resin composition of 8) was obtained.

The following evaluations were performed using this composition. The evaluation conditions are shown below.

(1) Extrusion moldability: Extrusion is performed using a 25 part m/ml axial extruder with a nozzle diameter of 0.5 mm and a medium extrusion rotation speed of 5 Orpm.The strand extruded from the nozzle is cut in 20 seconds and its length is measured. and the diameter (width) was measured. The shorter the length, the lower the drawdown property, and the wider the width, the better the die swell behavior, and the better the secondary processability.

Extrusion conditions: C, = 160°C, C, = 1.70°C, C
, = 180°C, D = 180°C, rotation speed = = 50 rpm (2) Stain resistance = kneading temperature 18 using a 6-inch roll
A 100 g sample was kneaded at 0°C with a roll spacing of 3mm, and the sheet was pressed at a pressing temperature of 180°C for 7 minutes to obtain a 5mm thick sheet with a good surface condition. The sample was measured using an automatic contact angle meter using water and oil (olive oil) by the droplet method at a temperature of 22°C at a constant dropping amount (speed), and the results were expressed as a contact angle θ. The larger the contact angle θ, the better the stain resistance.

(3) Breaking elongation at high temperature (120°C): A sheet made with a 6-inch roll was pressed at a pressing temperature of 180°C for 7 minutes to obtain a sheet with a 2-body thickness and a good surface condition. A D-type dowel piece (ISO No. 3 type) was prepared from the sample, and a tensile tester was used at 120°C.
A tensile test was conducted at a speed of 50 mm/min in an atmosphere of . The larger the elongation at break, the better the secondary processability.

(4) Appearance: The condition of the strand extruded by the extruder (surface characteristics, shine, gloss) The condition of the press-molded sheet was visually judged. The result is ◎ is the best and the following categories are ◎-〇, ○,
Indicated by △.

In a reaction vessel equipped with a stirrer and a reflux condenser, add 280 parts of ion-exchanged water and 1.0 parts of sodium dioctyl sulfosuccinate.
5 parts, 0° 2 parts of cumene hydroperoxide, 50 parts of methyl methacrylate, 30 parts of butyl acrylate, 3
,3,4,4,5,5,6,6,7,7,8,8,9,
9.10.10.10-Heptadecafluorodecyl methacrylate-h (17 parts M) 20 parts and n-octyl mercaptan (n-osh) 0.01 part were charged, and the inside of the container was replaced with nitrogen, After adding 0.2 parts of sodium formaldehyde sulfoxylate under stirring, the reaction vessel was heated to 70°C.
The temperature was raised to .degree. C., and the mixture was heated and stirred for 5 hours to complete the polymerization. After cooling the obtained polymer latex, aluminum chloride was added for salting out, followed by filtration, washing, and drying to obtain a polymer powder. The characteristics of the vinyl chloride resin composition blended with this polymer are shown below.
Shown in 1.

However, using the same reaction vessel as used in Example 1, a polymer was produced with the monomer composition shown in Table 1. Thereafter, salting out, filtration, washing and drying were carried out in the same manner as in Example 1 to obtain various polymer powders listed in Table 1. Table 1 shows the properties of vinyl chloride resin compositions containing these polymers.

Comparative Example 1 is a resin composition (blank) in which the fluorinated acrylic polymer of the present invention is not added to the vinyl chloride resin, but a stabilizer and the like are added. Its characteristics are shown in Table-1.

Using the same reaction vessel as that used in Example 1, a polymer was produced with the monomer composition shown in Table 1. Thereafter, salting out, filtration, washing, and drying were performed in the same manner as in Example 1 to obtain various polymer powders listed in Table 1. Table 1 shows the properties of vinyl chloride resin compositions containing these polymers.

(Left below) 1. Using the same reaction vessel as used in Example 1, add 280 parts of ion-exchanged water, 1.5 parts of sodium dioctyl sulfosuccinate, and 0.2 parts of cumene hydroperoxide.
After purging the inside of the container with nitrogen, 0.2 parts of sodium formaldehyde sulfoxylate was added under stirring, and the reaction container was heated to 70 parts.
The temperature was raised to 'C, and the mixture was heated and stirred for 3 hours to complete the first stage polymerization. Thereafter, in the presence of the obtained polymer, a mixture consisting of 10 parts of methyl methacrylate, 17 parts, 40 parts of M, and 0.005 parts of n-octyl mercaptan was added dropwise as the second stage monomer component over 3 hours. Then, the polymerization was completed in a further 3 hours to produce a two-stage polymer. Thereafter, salting out, filtration, washing, and drying were performed in the same manner as in Example 1 to obtain a polymer powder. Table 2 shows the properties of the vinyl chloride resin composition containing this polymer.

10-20 and ratios 5-7 Example 9 using the same reaction vessel used in Example 1
Various polymers were produced with the monomer compositions shown in Table 2 under the same polymerization conditions. Table 2 shows the characteristics of the vinyl chloride resin composition containing each polymer.

(Leaving space below) y1-day discharge Using the same reaction vessel as used in Example 1, add 280 parts of ion-exchanged water, 1.5 parts of sodium dioctyl sulfosuccinate, and 0.2 parts of cumene hydroperoxide.
parts and 10 parts of methyl methacrylate, 2.2.2-
After charging 20 parts of trifluoroethyl methacrylate (3FM) and purging the inside of the container with nitrogen, 0.2 parts of sodium formaldehyde sulfoquinate was added under stirring, and the reaction container was heated to 70°C for 3 hours. Heat and stir,
The stage polymerization was completed. Thereafter, in the presence of the obtained polymer, 30 parts of styrene, 20 parts of butyl acrylate, and 0.0 parts of n-octyl mercaptan were added as the second stage components.
1 part of the mixture was added dropwise over 3 hours, and the mixture was heated and stirred for 2 hours to complete the second stage polymerization. Thereafter, in the presence of the polymers obtained in the first and second stage polymerizations,
As the third component, 20 parts of methyl methacrylate was added dropwise over 2 hours, followed by heating and stirring for 3 hours to complete the third stage polymerization and produce a three stage polymer. Thereafter, salting out, filtration, washing, and drying were performed under the same conditions as in Example 1 to obtain a polymer powder. Table 3 shows the properties of a vinyl chloride resin composition containing this polymer.

4"22-35 and ratio 17 to 1 Using the same reaction vessel as used in Example j, a 3-stage polymerization was carried out under the same polymerization conditions as in Example 21 with the monomer composition shown in Table 3. The properties of the vinyl chloride resin composition blended with each polymer are shown in Table 3.

36-41 and ratio q Using the fluorinated acrylic polymer (three-stage polymer) obtained in Example 22, a vinyl chloride resin composition was prepared in the same manner as in Examples 1-35. The dyeability, extrusion moldability, elongation at break, and appearance of each of the three were measured.

However, the amount of the fluorinated acrylic polymer added was changed as shown in Table 1. The results are shown in Table 4 together with the results of Example 22.

(Margins below) 42-48 and ratio 1"l['1-16 100 parts of each of the following thermoplastic resins were blended with 3 parts of the polymer obtained in Example 22, and 3 parts of the polymer obtained in Example 22 were blended, and those were not blended, respectively, using a Henschel mixer. The resulting mixture was transferred to an l-screw extruder with a diameter of 5 mm.
The length and warp of each resin were measured for 20 seconds at the following different temperatures using a nozzle diameter of 0.5 mm and a constant rotation speed of 50 rpm. The results are shown in Table-5.

The shorter the strand length and the larger the warp (width) than the comparative product, the better the formability (drawdown property, tie swell behavior)
shows that it is good. In addition, the appearance of the strand was visually observed to evaluate the appearance.

(1) ABS resin (Diapet ■ABS#3001゜trade name, manufactured by Mitsubishi Rayon■) Molding temperature: C, = 1800C, C, = 200C, C3.
200°C, head = 200'C, die = 200'C (2) Styrene resin (styrene:\F-20, trade name, manufactured by Idemitsu Petrochemical ■) Molding temperature: C, = 160°C, C, = +80 °C,C,
・200°C, head = 200°C, die = 210
°C (3) Polycarbonate resin (Tsubashi Tsukufu 02
2 product name, manufactured by Mitsubishi Chemical Corporation) Molding temperature C, = 230°C, C, = 260°C, C, =
270°C, head = 270°C, die = 280°C (4) Polyethylene resin (Hisexfu 000F, trade name, manufactured by Mitsui Petrochemical Industries ■) Molding temperature: C1, 150°C, C, -165°C, C3・
175°C, head = 175°C, die 175°C (5) Polyester resin (Dyanite@PA-200
;Product name, manufactured by Mitsubishi Rayon■) Molding temperature・C1・280°C,C,=280℃,C,=
280'C, head = 260°C, die = 260°C (6) Vinyl chloride resin [Rhombic PVC (average degree of polymerization: 70
0)] Molding temperature: C, = 160°C, C, = 170°C, C
, = 180°C, head -175°C, die = 180°C (7) Polyphenylene ether resin (PPE) (Noryl 731, trade name, manufactured by GE Plastic ■) Molding temperature:
C, = 200°C, C, = 260'C, C, = 260°C
, head = 260°C, die / 260'C (Effects of the invention) Molding resin compositions in which the fluorinated acrylic polymer of the present invention is blended with various thermoplastic resins are superior to conventional unblended thermoplastic resins. t＼ Processability is good, secondary processability is excellent, molded products have excellent stain resistance (water repellency, oil repellency), gloss, etc. of molded products, and improvement in productivity is recognized.

Claims (1)

[Scope of Claims] 1. Contains at least one type of fluorinated alkyl acrylate unit and fluorinated alkyl methacrylate unit as all or a part of the polymer constitutional unit, and has a reduced viscosity ηsp/c (polymer 0.1 g An agent for improving processability and water and oil repellency of a thermoplastic resin comprising a fluorinated acrylic polymer having a fluorinated acrylic polymer having a coefficient of 2.0 or higher (measured at 25° C. when dissolved in 100 ml of chloroform). 2. Reduced viscosity ηsp/c (polymer 0.1 g) containing at least one type of fluorinated alkyl acrylate unit and fluorinated alkyl methacrylate unit as all or part of the polymer constitutional unit based on 100 parts by weight of the thermoplastic resin.
(dissolved in 100ml of chloroform and measured at 25°C)
A thermoplastic resin composition containing 0.1 to 20 parts by weight of a fluorinated acrylic polymer of 2.0 or more.