JPS5841995A - Production of new oil repellent paper - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a novel method for producing oil-repellent paper.

More specifically, there is a novel method for producing oil-repellent paper by processing paper with a phosphorus-containing organic fluorine-based polymer obtained from a vinyl monomer containing a fluoroalkyl group and a monomer containing a phosphoric acid group. Regarding.

Conventionally, glassine paper and PE laminated paper have been known as packaging paper for products containing oil, but in recent years oil-repellent paper treated with special organic fluorine compounds has been used. This utilizes the effect of an organic fluorine compound to impart surface energy, and the processed paper has the advantage of being breathable and easy to process.

Such organic fluorine compounds can be roughly classified into two types. The first compound is a perfluoroalkyl group-containing vinyl monomer in which hydrogen is completely replaced with fluorine, either alone or in combination with other monomers.

This is a compound that imparts water and oil repellency to fiber materials, and because it has water repellency, it is water-insoluble. These are emulsified and dispersed before use.

The second compound is a low-molecular surfactant in which a hydrophilic group is added to one or two perfluoroalkyl groups.

Furthermore, it is soluble in water to some extent and is expected to have oil repellent properties. There are two types of these: a type in which the hydrophilic group is a phosphate ester, and a type in which the hydrophilic group is a polyvalent metal chelate such as chromium of a carboxylic acid.

Since the former is a dispersion, it has poor compatibility with other paper processing chemicals such as sizing agents, and when used at high speeds, the dispersion is destroyed and blocks occur, causing unevenness and making it difficult to use. - It is difficult to use.

Among the latter, polyvalent metal chelate types whose hydrophilic group is a carboxylic acid such as chromium are limited in use due to the toxicity of the metal ion, and types whose hydrophilic group is a phosphate group are often put into practical use. .

In this perfluoroalkyl phosphate ester and its salt, the phosphoric acid group acts specifically on the perfluoroalkyl group, imparting hydrophilicity to the compound, and at the same time is well distributed to cellulose, resulting in the perfluoroalkyl group on the surface. They are arranged in a good manner and make the paper highly oil repellent.

However, perfluoroalkyl phosphate esters used as conventional oil repellents have the following problems.

First, perfluoroalkyl phosphate esters are prepared from the corresponding perfluoroalkyl alcohol and a phosphorylating agent such as phosphorus pentoxide, phosphorus trichloride, or phosphorus oxychloride.

However, side reactions such as perfluoroalkylnorogenide and perfluoroalkyl phosphate triester are produced, resulting in a low yield. This has the disadvantage that since the perfluoroalkyl compound is an expensive material, its influence on economic efficiency cannot be ignored.

Secondly, in addition to the ease of processing oil-repellent paper, users have various requests such as the degree of oil repellency, water repellency, size, breathability, and adhesive strength. The drug made by neutralizing the perfluoroalkyl phosphate ester of rice J and i with aqueous ammonia has a simple structure, and cannot be changed except by changing the number of fluorotetraalkyl groups and phosphate groups to change the balance. However, it is difficult to meet this demand by adding other paper finishing agents, and there is a drawback that the applications of oil-repellent paper treated with this agent cannot be expanded.

The present inventors focused on the usefulness of oil-repellent paper treated with organic fluorine compounds, and conducted extensive research into a method for producing oil-repellent paper that does not have the above-mentioned drawbacks, that is, can meet a wide range of demands in addition to being economical. Result 1 The present invention has been completed.

That is, the present invention provides (a) a perfluoroalkyl group-containing vinyl monomer (
However, R8 represents a hydrogen atom or a methyl group, and R3
represents a divalent bonding group in which an alkylene group having 6 or less carbon atoms or a substituted alkylene group, an ether group, an ester group, an amide group, etc. are connected, and n and m are 1.
Alternatively, it is 12, and n+m=5. M is hydrogen,
Represents an alkali metal atom, 1.2 and tertiary amine having 6 or less carbon atoms, or ammonia. This invention relates to a method for producing oil-repellent paper, characterized in that the paper is processed with an organic fluorine-based polymer obtained by copolymerizing a phosphoric acid group-containing monomer represented by the following formula.

The perfluoroalkyl group-containing vinyl monomer according to the present invention (a) is polymerized with a fluoroalkyl group having 4 or more carbon atoms, preferably 4 to 18 carbon atoms, in which hydrogen is replaced with a fluorine atom.
Any compound may be used as long as it has an unsaturated double bond. Examples include the following compounds.

(1) C Ding FtsCH! 0COCH=C&WC Hatake F,! 80. N (C Hatake Hma) CH CH, 0 COCH=
CH.

(3) CaFtySOtN(CL)CHtCHtO
COC(CHs)=CH2C11m=CHCOOCHt
C Mountain (5) C FtsCON (C YiHa) CHICHI
OCOC(CHs) =CHt(6)CFs(CFri5cHtc&0cOcH=cHt(7) CFa(C
Fa)+1CHtCHtOCH=CHz(8) C
aFty(CHrittOCOC(CHs)=CHtal
l (CFs)tcFo(C mountain)sOCOCH=CH
*CH,=CHC00 u CaFtySOFriendN(CHtCHmOCOCH=
CHt) Goose QI CaFtySOtN(CHsXCH
t) socOOcH1cH=cHtlI◆ CaF
nS OWN (C!H1)CHIC&0COCH=C
HC00C4Hea9 CsFtsSOmN(CHs
)CHtC&0COCH=CH*@* CsF+yS
OtNHC&CHmS (hCH"CL) Also, the phosphate group-containing monomer (b bond) of the above general formula, examples include the following compounds.

0 Mono(2-hydroxyethyl acrylate) acid 7
Male 7-acetate (structural formula above), mono(2-hydroxyethyl methacrylate) acid 7-osphatate, mono(2-hydroxyethyl acrylate) acid 7-osophate, mono(2-hydroxyethyl acrylate) acid 7-osphetate (2-hydroxypropyl methacrylate), mono(2- Hydroxyethyl vinyl ether→acid phosphate, mono(6-hydroxyglopyl methacrylamide) acid 7 oxphosphate, di(2-hydroxyethyl methacrylate) acid phosphate, perfluoroalkyl-containing vinyl monomer rat and phosphate group-containing Any proportion may be used as long as the copolymerized JtGL copolymer of monomer (b) is water-soluble or semi-dispersible and has excellent oil repellency, but the former is at least 25%
The ratio of the latter to 99 weight tS is preferably 1 to 75 weight, and particularly preferably the latter is 1 to 50 weight of the former 50 to 99 weight.

In order for the copolymer of the present invention to exhibit better oil repellency,
Alternatively, a hydrocarbon vinyl monomer may be copolymerized in addition to the above (touge (b)) for other purposes.

Examples of such hydrocarbon vinyl monomers include non-functional group monomers having carbon-carbon double bonds such as butadiene, isoprene, vinyl chloride, acrylonitrile, (meth)acrylic acid esters or amides, and N- methylol acrylamide, β-hydroxyethyl methacrylate,
Examples include functional group-containing monomers having a carbon-carbon double bond such as glycidyl methacrylate. The copolymerization weight ratio of these hydrocarbon vinyl monomers is the perfluoroalkyl-containing vinyl monomer tat and the phosphoric acid group-containing monomer (b
) should be less than 50 times '1jk-.

If it exceeds 50% by weight, the oil repellency of the copolymer of the present invention will deteriorate.

The copolymer of the present invention can be easily obtained by a known method of vinyl polymerization, for example by using a radical initiator, but generally 400 or more is preferred.

As described above, the present organic fluoropolymer can be made by changing the type and amount of the monomer, the type and amount of the terpolymer, and the molecular weight. By freely changing the balance of phosphoric acid groups, it is possible to produce oil-repellent paper that can meet a wide variety of needs.

The phosphoric acid groups of the fluoropolymer of the present invention may be neutralized with amines such as ammonia or bases such as caustic soda to increase hydrophilicity or for other purposes. The fluoropolymer of the present invention can be used for oil-repellent treatment on paper either by surface treatment or internal treatment (internal addition) as a mixed solution of water or a water-soluble organic bath agent, or as a dispersion with an emulsifier. Served. Of course, in addition to the present fluoropolymer, the processing fluid may also contain various curing agents such as amino resins and epoxy resins, various sizing agents, various pigments, and various adhesives.

A promising oil-repellent paper according to the present invention can be produced by changing processing conditions such as increasing or decreasing the amount of the fluoropolymer treated.

Further, the paper referred to in the present invention may be any material as long as it is made of fibrous material, but paper used for packaging etc. is preferable.

In order to make the present invention more clear, the present invention will be described in detail using Examples below. Note that parts in the examples are based on weight.

Example-1 50 with a sprayer, temperature needle, and nitrogen gas introduction tube set
0-4 round flask K Cm Fu S Ox N (
Cm Hy ) CH, CH4C0CH=CH, 72 g of perfluoroalkyl-containing monomer, 8 g of mono(2- and droxyethyl methacrylate) acid phosphate as a phosphoric acid group-containing monomer, and as a polymerization regulator. Lacryl mercabutane [12tI, isopropyl alcohol 120y as a solvent, and azobisisobutyronitrile ctaII as a polymerization initiator were added, and the mixture was heated and stirred at 70°C for 6 hours to obtain a viscous translucent solution. Into this 10. ? 30-ammonia aqueous solution was added thereto, and then pure water was added to make the total weight 5009.

This compound was processed into various papers using an internal addition method, and the oil repellent effect was tested.

Examples 2 and 6 The ratio of 72 parts of the perfluoroalkyl-containing monomer of Example 1 to 8 parts of moha(2-hydroxyethyl methacrylate) acid 7 phosphate was changed to 60 parts to 20 parts and 4 parts.
The synthesis was performed under exactly the same conditions as in Example 1 except that the ratio was changed from 0 parts to 40 parts, and the evaluation is shown in Table 21.

Adjustment of test solution (Mol, ratio) Drying conditions: normal temperature Sizing degree Example according to JIS P-8122 -
4 50 with stirrer, temperature needle, and nitrogen gas introduction tube set
Qm4 Tsuro 7 Lasco KCaFtySOzN (CHs
) CHtCH*OCOC(CHs) = perfluoroalkyl-containing monomer 40Ii which is expressed in CHz and mono(3-chloro-2-hydroxyethyl methacrylate) acid 7 osphene as a phosphate group-containing monomer) 10, 9 and 2-hydroxyethyl methacrylate say, lauryl mercaptan Q, 21I as a polymerization modifier, inglobil alcohol 12 as a solvent.
Furthermore, azobisisobutyronitrile tOI was added as a polymerization initiator, and the mixture was heated and stirred at 70° C. for 6 hours to obtain a viscous translucent solution. Among these, hetriethanolamine 5
y and then pure water were added to make c#1 weight 500 I. The results of processing this polymer salt by the internal addition method are shown in Table 2.

Example-5 Mono(6-chloro-2-hydroxypropyl methacrylate) acid 7mose 7ate 10g to 50g 2-
Hydroxyethyl methacrylate A viscous translucent solution was prepared in the same manner as in Example 4 except that 60I was changed to 10P. This oil repellency is also listed in Table-2. In addition,
The conditions of this experiment were exactly the same as in Table-1.

Example-6 50 with stirrer, temperature needle, and nitrogen gas introduction tube set
C6F1480tN (C1Hy
) CH2CH2OCOC(Cus)” perfluoroalkyl group-containing monomer 609K represented by CHt,
Mono(6-chloro-2-hydroxypropyl methacrylate) acid 7 osphene) 20,9 and 2-ethylhexyl ivy acrylate as phosphoric acid-containing monomers
) 2ON, lacryl mercaptan α21. as a polymerization regulator. Isopropyl alcohol 120I as a solvent
Furthermore, as a polymerization initiator, azobisisobutyronide lJ/
The mixture was heated and stirred at 70°C for 6 hours to obtain a dispersion. A 30-ammonia aqueous solution of 109 was put into this, and then pure water was added to make a good dispersion with a total weight of 500 g.The surface of paper was treated with the nine-polymer salt, and the oil repellent effect test results are shown in Table 3. Shown below.

Table-6 Zμx paper (#95%) Kraft paper (#
95%) Squeezing Al: Rubber roll Drying conditions: Room temperature

Claims (1)

[Claims] (a) Perfluoroalkyl group-containing vinyl monomer (
However, R7 represents a hydrogen atom or a methyl group, and R7
represents an alkylene group or substituted alkyne group having 6 or less carbon atoms, or a divalent bonding group in which these are connected to an ether group, ester group, amide group, etc., n and m are 1 or 2, and m10m=3. M represents hydrogen, an alkali metal atom, 1.2 or tertiary amine having carbon a3 or less, or ammonia. ) A method for producing oil-repellent paper, which comprises processing paper with an organic fluorine-based polymer obtained by copolymerizing a phosphoric acid group-containing monomer.