JPS5993706A - Preparation of vinylidene chloride copolymer latex - Google Patents

Abstract

PURPOSE:To obtain the titled latex having excellent coating properties, by polymerizing vinylidene chloride, etc. in the presence of an anionic emulsifier, adding vinylidene chloride, acrylic acid, etc. and a comonomer to the obtained latex, and subjecting the mixture to the emulsion polymerization in the presence of a specific polymerizable emulsifier. CONSTITUTION:(A) 5-80pts.wt. of a monomer mixture composed of 50-95wt% of vinylidene chloride and 5-50wt% of a monomer copolymerizable therewith is emulsion polymerized in the presence of (B) 0.01-0.3pt.wt. of an anionic emulsifier. The obtained latex is added with (C) 20-95pts.wt. (the sum of the monomers is 100pts.wt.) of a monomer mixture composed of 50-95wt% of vinylidene chloride, 0.5-15wt% of one or more monomers such as (meth)acrylic acid, glycidyl (meth)acrylate, etc. and 4.5-49.5wt% of a monomer copolymerizable therewith, and the whole mixture is subjected to the emulsion polymerization in the presence of (D) 0.1-30pts.wt. of a polymerizable emulsifier such as sodium styrenesulfonate, sodium alkylallylsulfosuccinate, etc.

Description

[Detailed description of the invention]

The present invention relates to a method for producing a jA'+f vinylidene copolymer latex having good coating properties. Generally, synthetic latex is hydrophobic, so in order to make it a stable water dispersion, it is necessary to use a surfactant or make the surface of the dispersed particles of synthetic resin hydrophilic. It is. Generally, it is easier to produce aqueous dispersions using surfactants, but although the presence of this surfactant is essential for the nature of aqueous dispersions, once they have been processed, they cannot be easily processed. Therefore, it is best to use as little surfactant as possible.The same is true for vinylidene chloride copolymer latex, and in a coated film applied to a plastic film, the amount of surfactant The presence of such substances may cause inconveniences such as deterioration of gas barrier properties, water absorption and whitening, and deterioration of contact properties.

[I'm going to live. Therefore, there is a method of polymerizing with less amount of 71J agent, but this increases the latex particle size, but there are major issues such as the fact that the mechanical stability of the latex deteriorates significantly and that the object to be coated cannot be coated with Jθ-. On the other hand, a method of polymerizing without an emulsifier is also known. / Kotoe describes the polymerization of styrene with I'l: 5 as a starter.
It has been reported that stable polystyrene emulsions can be obtained without using potassium oxide. However, with this method, the solid content is increased to 7/::.
[This is a fatal drawback in practice. In the copolymerization of vinylidene chloride and a functional monomer, the present inventors have discovered that by using a polymerization-reactive emulsifier having a double-bonded vinyl group, 1. It was discovered that a latex with good elasticity can be made without struggling, and the present invention was achieved. The feature of the present invention is that as a first step, vinylidene chloride 50~
95% by weight, 5 to 5 monomers copolymerizable with vinylidene chloride
Monomer mixture consisting of 50% by weight 5-80% by weight〒4]S
is emulsion copolymerized in the presence of ~0.3 parts by weight of anionic emulsifier o, oi, and the second step b',! To the latex obtained as J, add Nl (vinylidene chloride 50 to 95% by weight, acrylic acid, methacrylic acid. At least one monophase selected from glycidyl acrylate and glycidyl methacrylate: 0.5 to 15% by weight). Takeover%,
Monomers copolymerizable with these: 4.5 to 49.5 weight 1λ%
16 parts by weight of a monomer mixture consisting of 2D~95 weight (unit weight of the first stage monomer and second stage monomer: total of 100 parts by weight) is added, and sodium styrene sulfonate, Coatability is improved by emulsion polymerization in the presence of an alkyl-reactive emulsifier of 0.1 to 6.0%. Good 7 [
The purpose is to produce vinylidene chloride copolymer latex. The present invention will be explained in detail below. The first step of polymerization is: (vinyl chloride 50-9
Pentamer: % Preferably 60 to 93% by weight, 5 to 50% by weight of a mono-H1 body copolymerizable with vinylidene chloride, preferably 7 to 40% by weight of a mixture of monomers, preferably 5 to 80% by weight Part of the bite is 10-70'ji3: f;:I'll
Examples of monomers copolymerizable with vinylidene chloride include methyl acrylate, acrylic 1')Q ethyl, propyl acrylate, acrylic ammonium butyl, acrylic f', Q2-ethylhexyl, and acrylic octyl. Methacryl 1 methyl, acrylonitrile 1 iAlized vinyl vinegar 1'; The body can be suitably used +111 with Jl"l'i'. Acrylic l of both speeds:"I"f: #Methacrylic I"
y": Glycidyl as acrylic. Functional monomers such as glycidyl methacrylate are viscous and the particle size of latex ()1
(Excluded from the viewpoint of safety stability. If No. s1 vinylidene pentide is less than 50% by weight, the gas barrier properties, which are the special properties of vinylidene chloride copolymer latex, etc., will be impaired. On the other hand, if the content exceeds 95% by weight, crystallization occurs prematurely after latex production, impairing the properties of the latex. Examples of ionic emulsifiers include sodium dodecylbenzene sulfonate, sodium lauryl sulfonate, and alkylnaphthalene sulfonate. Sodium, alkyldiphenyl ether disulfonated soda, dialkyl sulfosuccinic soda, etc. are preferably used (12).
(It is used within the range of 0.01.ill, but if it is less than 0.01.ill, the mechanical stability of the latex will be impaired. If it is more than 0.60.0000, the particle size of the latex will only become smaller.) Instead, a free emulsifier exists in the latex, and IJψ water whitening etc. will not occur, and the physical properties will be 4i1.In addition, the surface tension of the latex will be lower, which is favorable for coating R;%. Now, the monomer mixture described above is emulsion polymerized in the presence of 5 to 8 parts of anionic emulsifier, but the monomer mixture is As the amount of the polymer in the polymer mixture increases, it is desirable to increase the amount of the anionic emulsifier in 1.IHiii above. 517j
Nezubumi 11.1. If it is 1, the latex particle size can be controlled by 1! :I :')III; becomes. On the other hand, 80
Adding 4 parts of heavy JII to il'X'i impairs the mechanical stability of the latex. 21st power, )゛, Emulsion polymerization is preferably a vinylidene chloride co-herbal polymer obtained by emulsion polymerization of the above first stage 1.Niji 5 to 8D weight part i'J: 1 [ ] to 70 weight parts In the presence of a latex containing 2 parts, a polymerization-reactive emulsifier of styrene sulfone soda or alkylaryl sulfoconophosphate sodium phosphate, preferably 0.1 to 3.077 parts, is added.
．． Use 2 to 20 parts, vinylidene chloride 50 to 95
Heavy - good % good or 60-93 city - clear %, acrylic acid,
Methacrylic acid, glycidyl acrylate. glycidyl methacrylate, at least I
J+, i monomer 05-15 weight'f? C% good luck 1
．． 0 to 10% by weight, and a copolymerizable monomer mixture consisting of 45 to 495% by weight, preferably 6 to 69% by weight); 1% to 20 to 95% by weight. Or 60-9
The functional monomer used in the present invention is acrylic acid. At least one of methacrylic acid, glycidyl acrylate, and glycidyl methacrylate. If the amount is less than 0.5 weight - j11%, the 61.i resistance of the latex is poor, while if it exceeds 15 weight - h17%, the gas barrier properties tend to deteriorate. In addition, the type of monomer copolymerizable with vinylidene chloride and the self-functional monomer is preferably the one used in the 11th polymerization +r+'r. Using a polymerization-reactive emulsifier with double bonds without using an emulsifier with
It is an essential requirement for invention. As a polymerization-reactive emulsifier, styrene sulfone n'& sokylaryl sodium sulfosuccinate CCH2' = CH・ci-i,・OOC-CD (
CI-12COOI(,)80BNα, R is rotational prime number 1~
At least one type selected from 18 alkyl groups is used in an amount of 01 to 60 parts by weight. By using this polymerization-reactive emulsifier within the above-mentioned range, it imparts hydrophilicity to the latex particles without impairing mechanical stability.
Since no general emulsifier is used at this stage, coating 11!2I'
l We will not put anyone at a disadvantage. Polymerization Reaction 1-1 If the emulsifier contains less than 16-0, the mechanical stability of the latex will be impaired, and if it exceeds 3.077 parts, the combined parts will be modified and the gas barrier properties will deteriorate. . V4s 1 + polymerization and the amount of monomer used in the second stage are 100 parts by weight in total, but the amount of intermediate used in the second stage polymerization is 20 parts by weight. On the other hand, if the weight exceeds 95 weight, the control of the particle size of the latex becomes conical.The amount of water used is 100 to 600 weight ↑zi (but Preferably, the particle size of the latex of the present invention is preferably in the range f71T of 800 to 200 OA from the viewpoint of coating properties.The conditions for the catalyst double polymerization used are the same as the catalyst double polymerization conditions for ordinary emulsion polymerization. Silica, wax, pigments, etc. can be added to the latex of the present invention.Furthermore, even if it is diluted with a water-soluble organic solvent such as alcohol, the stability of the latex is impaired. The vinylidene chloride combined latex obtained in the present invention has a relatively low amount of free emulsifier, has a high surface tension, and has excellent elasticity for coated materials. It is a latex with very good coating properties. Therefore, the latex of the present invention can be coated on paper using a conventional air knife coater, doctor grate coater, roll coater, etc.
It can be easily applied to glass films, etc., and the physical properties of the resulting coating film are free from boiling and whitening.
It has extremely low oxygen permeability and excellent mechanical stability. It can also be widely used as an adhesive. The advantages of the present invention will be shown below using actual M'A examples. In the Examples and Comparative Examples, %2 parts is -% by weight. Weight First, the evaluation test method will be described. (1) Coating property of latex After polymerization, alcohol (methanol, ethanol, Improvil' alcohol), or 50% alcohol aqueous solution 7 (
Dilute the solid content of 77.1 degrees with distilled water and add 10% beads, and then remove the surface [clear treatment J-'li 2 if'l! 1 Stretched polypropylene film with 1 hardness (y, 1 height as minute, °“
Apply it so that it becomes 8 o'c cv F! It was dried in a cold oven for 60 seconds. The coated film was evaluated as good if it had no spotty repellency, cracks, or whitening. (2) Boil whitening surface 1 "Nogized 2R?! + Stretched propylene film with polyurethane adhesive (Toyo Morton Co., Ltd.; I
i'! , Olipine EL-250) vinegar 13'doethyl i'? F+: Coat the sample latex to a solid content of 06'/yrr and dry in a hot air oven at 80'C for 60 seconds.
%, ·, and dried at 80"C for 60 seconds, then aged at 4"Ll"C for 48 hours. The coated film was soaked in boiling water at 95°C for 60
The degree of whitening of the film was observed with the naked eye after a few minutes of use. Those with no whitening were rated as good, those with a slightly pale, fluorescent color were rated as slightly poor, and those with whitening were rated as poor. (3), MOCO using the sample used for the boil whitening test of oxygen permeability (2)
NO OX-'1"RAN-100 (to 4odern
Example 1 A pressure-resistant glass 11 autoclave with a stirring blade (=J) was heated after replacing the viscous gas with IPc. Deionized water as the first stage
120 parts Rubensense Rubensen Soda D, 2 // Excess Potassium
Oo2 Sodium hydrogen sulfite
Oo1〃PVC, nylidene
64.4 // Acrylic ri? methyl
Prepare 56〃, 45°C, 200? -1 at 711
Polymerization occurred at 5:00 a.m. in January. As a second step, sodium styrene sulfonate 10 parts deionized water 5 "t=i'f hibinylidene 27 WiS acrylic)
)・Methyl 21 〃Methacrylic 1”
iQ, rJ, 9 IIJ! 1
1%! Shit□nononorium
[j, 01//41j 1Ail 111<Hydrogen soda 0.
Add 005// to i′・, add 11 ml of Arashi, add 45”C, and then mix for 1511; in a way (i
(The results of the trial of l'jj film were shown to 4.1 people. 5 no 5 no) 111 Example 2 ■ ,1. Made of pressure-resistant glass with 11 blades! After the autoclave was removed, the first step was +1 + 1X ionized water 10 [] parts Sodium argyl diphenyl ether disulfonate 0.05//
Fu Δ″ sweat (c ``Kano potassium 0.
01//Ai1 Pheasant Hydrogen Soda 0
．． 005//vinylidene chloride 18
4 Acrylic (″12 methyl 1.
6) and heated at 45°C, 1200rpyn for 10 hours 9
Polymerization took place in January. After that, as the second stage, add Alkylaryl Sulfosucci 1j/7 Soda 2.
0 7; l≦monthly, -ionized water
25 1. Vinylidene iride
72. Ott acrylic! i(2 ester
56 〃Methacrylic self 22.4 "51' Rorufi: FI11' Potassium
0.01// ([m f aqua slag, soda
[], 005// was added afterwards, 45°
C. for a further 20 hours to polymerize. Click + for the test results of this latex coated film.
It is shown in Table 1. Example 6 Pressure-resistant glass with 15 stirring blades; i, 21e autoclaved with deionized water as the first stage after exchanging the autoclave with nitrogen.
90 7:l! Sodium alkyl diphenyl ether disulfonate 01 i&M potassium sulfate IJ, CJ'l//ill
(T I 5 Sansui 5 and soda 0.00
5 //+7. Vinylidene Xide 64
．． 8 r':'J acrylic fylmethyl
4. o〃Methacrino-2 methyl 1
No. 82 was prepared and mixed at 45° C. and 120 rpm for 15 hours at 1'f'. 2 ``As a first step, Il too; 5 parts of ionized water, 1,11, and 0.01//Akyūr・Jōsuien;;Soda (1005zz
I did Taka. After that, deionized water 6o Chang: S styrene sulfone l"jlj soda D, 5〃 and vinylidene chloride 52.28B acrylic 1゛1-limethyl 54〃methacrylic acid 1.8〃glycidyl methacrylate 0.6〃 were added over 6 hours. Continuously added using a metering pump. Then stirred for an additional 4 hours fp,':
The polymerization was completed. The test results for this latex coated film are shown in Table 1. Examples Polymerization was carried out in the same manner as in Example 6, with the emulsifier and monomer compositions of the ζ11th stage and the second stage changed as follows. 1st stage Sodium lauryl sulfate 02 parts Vinylidene M 46.07/Acrylonitrile 1.0//Methyl acrylate
3. o〃Nail (2 [;Dome Alkylaryl Sulfosucci e Soda 1.0 parts Vinylidene chloride 42.5//Acrylic j Minoh methyl 65〃Acrylic Minami
1.5 Glycidyl methacrylate
2.5 The test results for the coated film of this latex are shown in Table 1. Comparative Example 1 Polymerization was carried out in the same manner as in Example 2, except that the emulsifiers in the 281st and 211th stages were changed as follows. 1'kun 1st stage dodecylbenzenesulfone 112 soda o, 2 parts; +
s 2nd stage dodecylbenzene sulfone soda O,a +<+S
The surface tension of the latex was 48 d'In 1.7/c0. When this latex was diluted by adding alcohol or a 50% alcohol water bath, the latex was destroyed. When diluted with distilled water, the surface of latex
The force is 52 ”/rL/(3, K 7; c ′), 2 i
iiIM: When applied to the water-repellent surface of stretched polypropylene film, repellency occurred and uniform application was not possible. Dodecylbenzene sulfone 1. When 06 parts of soda was added, the surface tension was 41 d, yn,
I was able to apply the film without needing to repel it on the hot millipropylene film, but after drying it in a hot air oven, I observed that the coated film had two white spots and there were many cracks. Comparative Example 2 Polymerization was carried out in the same manner as in Example 2, changing the emulsifiers in the 1st stage and 1°!'52nd stage as follows. 2. I2nd row Alkylaryl sulfosuccinic acid I'l'2/l-
0-5 +31'+Test R of the coated film of Comparative Example 2
'Q results show that 201 balls and 1 ball have good warp properties. Comparative examples show that when using an anionic emulsifier and polymerization reactivity ≧ b emulsifier frost ゛ is outside of the present invention I... There were cracks, 7 cracks appeared, and boil whitening was also defective. Procedural amendment February 9, 1980 Director General of the Japan Patent Office 1, Indication of the case 1982 Patent Application No. 205418 2. Name of the invention - 1. Method for distributing vinylidene chloride symbiotic latex 3
, Relationship with the case of the person making the amendment Applicant 4, Agent 111 Chiyo, Tokyo] No. 401 A, 2-106-2, Marunouchi-ku
Room 6, subject of amendment 'J' M (l t, + invention N: Iyllll ii, lW Q'J column 7, content of amendment (1), details!) 3rd government, line 7 'i (2), page 3, line 12, 1-Ffl, rTJ, It says, ``Wa, two wheels combine,'' and it says, ``Fu 1 < shiwa ji, ``[self-koai]'' and tears. (3). [How dare you, you're such an idiot!'' 1st iTh L First. (5), same; 1'14 Yoshiman line 6, "acrylic [drop-ester]" was first corrected as [acrylic 1 ")・?methyl]. (6), same no. 17 @ line 12 [r] 9 water treatment] 111”
and 4b is revised to ``1 oxidation treated surface''. (Power, same r; p; t9 Tei table 1 preparation jp, , W body preparation i) 4. ' 1 j stitch, single 1 of surname example 3. ) body Fv
+No I ~ IA MA7 to j and Ruru wo [VD JviA
MMA J and i-i:r j "L:'r:zu. I-] Two procedural amendments Director General of the Japan Patent Office 1, Indication of case 1982 Patent Application No. 2034J8 2, Name of invention Vinylidene chloride Copolymer latex manufacturing method 3, relationship with the case of the person making the amendment Applicant 4, agent 401-2-6-2 Marunouchi, Chiyo 111-ku, Tokyo Room 5 Date of amendment order Showa year time(
1) Insert the following item next to Table 1 on page 19 of the details box. Example Contents of 2 felt 91 stretch blow molded from polyethylene terephthalate in the latex obtained in Example 4 (
The outside of the bottle was immersed up to the back neck of No. 111 without corona discharge treatment, and the bottle was pulled up horizontally and rotated at 20 ORPM around the center of the mouth and bottom of the bottle to remove excess latex. Dry with hot air at °C for 2 minutes. No cracks or whitening were observed on the coated surface. Thereafter, it was aged at 40°C for 48 hours 1' and 41 hours. A cellophane adhesive tape was applied to the latex coated surface and then strongly pulled off, but the vinylidene chloride and 11 combined layer did not show any damage. Next, as a water-resistant adhesion test, the bottle was filled with water up to the neck.
It was released for 20 minutes at 0'C. In the same manner as above, a cellophane adhesive tape was brought into close contact with the latex-coated surface and strongly peeled off, but the vinylidene chloride copolymer layer was not peeled off. It can be seen that the vinylidene j' copolymer latex of the present invention strongly adheres to oxidized polyethylene terephthalate 1111. Fruit 1', (,, Example 2 Actual power fj In the latex obtained in Example 4, after applying corona discharge treatment to the outside of the bottle with the inner axle 11, which was blow molded from polypropylene, -6"J was applied to the neck of 3tJL, and 11 °j)
Hold the Crab Pull JIIj horizontally, rotate it at 200°)(,f%l) around the center of the mouth and bottom of the )'Jr, remove excess latex, and heat it at 60°C with a wind blower. No spot-like repellency, cracking, or whitening was observed in the direction of application.Then it was kept at 40°C for 48 hours.
#lj I did it. A cellophane adhesive tape was placed in close contact with the latex coating and was strongly peeled off, but the vinylidene chloride copolymer layer was not peeled off. Next, fill the bottle with water at the neck and let it air at 20°C for 2 days.
°I did. Subsequently, in the same manner as above, a cellophane adhesive tape was closely attached to the latex coated surface and then strongly peeled off, but the vinylidene chloride copolymer layer was not peeled off. It can be seen that the vinylidene chloride copolymer latex of the present invention strongly adheres to the oxidized surface of polypropylene. EXAMPLES Using the latex obtained in Comparative Example 1 and a bottle made of biaxial stretch blow molding from polyethylene terephthalate, the latex was applied in the same manner as in Experimental Example 1 and dried. Aged. It was difficult to apply uniformly because of the crinkling that occurred when removing the coating.Also, when a cellophane adhesive tape was tightly threaded on the latex coated surface of (m) and strongly peeled off, vinylidene chloride and IF were removed.
The combined layer peels off easily: "jlML/ta."

Claims (1)

[Claims] 1≦1 (vinyritine chloride 50-95% + ”: F□
5 to 50 monomers copolymerizable with l'r-vinylidene 1
5-80 parts by weight of lj'Lfjj body 8ij consisting of 3% 1=, S ion emulsifier DC1-Q, 57u-emulsified in the presence of a needle, and the resulting 1% latex was mixed with cyclized vinylitine. 50~95%) Acrylic T'l'l:
P methacrylic acid, acrylic 1-12 glycidyl, glycidyl methacrylate (at least one type of monomer (i-isomer 05-15 1%); monomer copolymerizable with these 4.5-1%) 49.5℃u1:
Single product consisting of % and 20 to 95 parts by weight of thermocompound (single (
(100 parts by weight) and 0.1 to 3.0 parts by weight of at least one γ11-reactive emulsifier selected from styrene sulfone soda and alkylaryl sulfosuccinic acid soda. f;'' (811 production flow of vinylidene chloride copolymer latex with good coating properties characterized by emulsification and combination in the presence of 7Sl'+)