JPS60139896A - Size composition - 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 sizing composition, and more particularly, it has an improved sizing effect, eliminates paper machine contamination,
Regarding size and composition.

Conventionally, starches such as potato and sweet potato have been used as sizing agents for paper sizing, but the sizing effect is not sufficient. Therefore, it has been proposed to use cationic starches obtained by treating these starches with cationic modifiers such as halogenated alkylammonium salts, monohalogenated alkylamine salts, etc., but this method is still not fully satisfactory. I haven't gotten anything to know. On the other hand, a size composition made by combining these cationic starches with alkenylconophosphate anhydride (neutral sizing agent) is also known (Japanese Patent Application Laid-open No. 197397/1983), but this size composition also has a sizing effect. However, there was an inconvenience that the hydrolyzate of alkenyl anhydride and phosphoric acid contaminated the paper machine.

The present inventors have conducted extensive research in order to eliminate the above-mentioned conventional drawbacks. As a result, among cationic starches, those having a specific value for the product of viscosity and degree of cation substitution can better fix the neutral sizing agent to cellulose fibers, improving the performance of the neutral sizing agent. They discovered that it is possible to do this without contaminating the paper machine, and have completed the present invention. ... ・□ That is, the present invention uses cations whose product of the viscosity (centipoise) of a 3% aqueous solution at 50°C and the degree of cation substitution (the number of moles of the substituent per mole of glucose residue) is 6 to 14. The present invention provides a size and a composition comprising a neutral sizing agent and a neutral sizing agent.

There are no particular restrictions on the cationic starch, and those obtained by various known methods can be used. For example, potatoes, sweet potatoes, and corn.

There are some products obtained by treating tapioca, wheat, and other starches with a cationic denaturing agent. Here, the cation modifiers include halogenated alkyl ammonium salts, halogenated alkyl amines, halogenated alkyl diamines, epoxidized alkylammonium salts, epoxidized alkyl amines, aminoethyl sulfuric acid, ethyleneimile, sulfurium, /anamide, Examples include alkali metal cyanamides and alkaline earth metal cyanamides.

In addition, other cationic starches include those obtained by reacting the above starches with epichlorohydrin and then alkylamine, and those obtained by ether-bonding acrylamide and then subjecting it to Hoffmann decomposition or Mannich reaction. and (2) those obtained by adding acrylonitrile and then hydrogenating them.

The first component of the present invention is composed of cationic starches having a product of viscosity and degree of cation substitution within a range of 6 to 14.

Here, the viscosity of the cationic starch is based on a 3% aqueous solution of cationic starch at 50° C., and the unit is centipoise (cps).

Further, the degree of cation substitution indicates the degree of cationization of starch, and indicates the number of moles of substituents per mole of glucose residue. For example, the degree of cation substitution is 0.
05'5 indicates that 55 hydroxyl groups out of 1000 glucose residues are cationized.

The first component of the present invention may be one in which the product of the cationic starch viscosity (cps) and the degree of cation substitution as described above is within the range of 6 to 14. The degree of ion substitution is not particularly limited. Usually, the viscosity of cationic starch is 3 to 3000 cps, so it is selected appropriately from among these. In addition, the degree of cation substitution is usually 0
．． 01 to 0.08, from among these, one whose product with the viscosity of the cationic starch is 6 to 14 is appropriately selected.

If the product of viscosity and degree of cation substitution is outside the above range, it is not preferable because the sizing effect cannot be sufficiently improved.

The first component of the size composition of the present invention is to prepare a 3% aqueous solution of the starch at 50°C in order to cationize the starch.
It can be obtained by operating such that the product of the viscosity (cps) and the degree of cation substitution falls within the above range. This operation can be easily carried out by a conventional method, and the degree of cation substitution may be adjusted as appropriate depending on the viscosity of the starch used.

Next, the neutral sizing agent which is the second component of the present invention is not particularly limited, and various known ones can be used. Specific examples include alkenyl succinic anhydride, alkyl ketene dimer, alkyl ketene dimer derivative, isocyanate aziridine derivative, cono-phosphoric acid imide derivative, rosin anhydride, carbonyl derivative, fatty acid anhydride and the like.

Here, the amount of the neutral sizing agent blended is usually 0.05 to 1.0% by weight based on the solid content of the valve. The amount of cationic starch, which is the first component, is usually 0.2 to 2.0% by weight based on the solid content of the bulb.

In addition, in the present invention, an emulsifying agent and a filler 2 may be added as necessary.
It is also possible to use additives such as retention improvers.

Emulsifiers include nonionic emulsifiers, anionic emulsifiers,
Examples include cationic emulsifiers, and these can be used alone or in combination.

Any known nonionic emulsifier can be used, such as polyoxyethylene ether emulsifiers such as polyoxyethylene alkyl ether, holoxyethylene alkylphenyl ether, polyoxyethylene aralkyl phenyl ether, sorbitan fatty acid ester, and polyoxyethylene. Sorbitan emulsifiers such as sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene alkylamine,
Examples include polyoxyethylene fatty acid ester, glycerin fatty acid ester, oxyethylene oxyzolopyrene block copolymer, and the like. Examples of anionic emulsifiers include sodium polyoxyethylene alkyl ether sulfate and sodium polyoxyethylene alkyl phenyl ether sulfate.

Examples include sodium alkyl sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, and alkyl triethanolamine sulfate. Examples of cationic emulsifiers include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, and alkylbenzyldimethylammonium chloride.

Examples of fillers include heavy calcium carbonate, talc, clay, zinc oxide, diatomaceous earth, and barium sulfate.

Further, retention aids include cationic polyacrylamide and the like.

Paper making using the size composition of the present invention may be carried out in exactly the same manner as when using known sizing agents. One example of how to use the sizing composition of the present invention will be described. First, water is gradually added to the composition until the sizing agent concentration reaches 20%, and the composition is stirred to form an emulsion. Then dilute to 0.5%. Next, for example, 0.5%L
HKP (La u b Holz Kraft Pu1
Add the emulsion to a pulp slurry such as p),
Further, appropriate amounts of various additives are added as necessary, and then paper is made. Furthermore, the humidity is adjusted as necessary to obtain the product. Measure the size of this product to find out the size effect.

In the present invention, among cationic starches, a starch having a specific product of viscosity and degree of cation substitution is used, so that the neutral sizing agent can be well fixed on the cellulose fibers, and the neutral size The performance of the agent can be further improved. Therefore, according to the present invention, it is possible to further improve the sizing effect and eliminate contamination of the paper machine compared to the conventional method.

Therefore, the present invention can be effectively used in the paper industry.

Next, the present invention will be explained by examples.

Synthesis Example 1 (Synthesis of cationic starch) 100 parts by weight of cornstarch, 50 parts by weight of water.

10 Lffim part of a 3 wt% NaOH aqueous solution and the most part of diethylamine ethyl chloride hydrochloride type 4 were mixed uniformly, and the total amount was adjusted to 12.1.Then, the reaction was carried out at a temperature of 40°C for 8 hours. After adjusting to H3 with hydrochloric acid, it was dried with hot air at 40°C to obtain cationic starch. The degree of substitution of this cationic starch was 0.050, and the viscosity of the 3% aqueous solution at 50°C was 141 cps.

Synthesis example 2 100 parts by weight of cornstarch, 50 parts by weight of water.

100 parts by weight of a 3% by weight aqueous NaOH solution and 2.5 parts by weight of 3-chloro-2-hydroxyzolopyltrimedyl ammonium chloride were uniformly mixed,
．． Adjusted to 1. Thereafter, cationic starch was obtained in the same manner as in Synthesis Example 1. The degree of substitution of this cationic starch was 0.027, and the viscosity of the 3% aqueous solution at 50°C was 480 cps.

Example 1 Too many parts by weight of a substituted cyclic dicarboxylic anhydride (neutral sizing agent Add 3 parts by weight of a certain octyl polyoxyethylene polyoxyzolopyrene ether sulfate sodium salt, and emulsify by hand stirring while adding water to obtain a sizing emulsion.

Next, the above sizing emulsion, cationic starch aqueous solution (Nippon Shokuhin Kako ■, Neotac 115D'), and heavy calcium carbonate (filler) were added to 0.5% Parzo suspension adjusted to -7.5 with baking soda. ) and cationic polyacrylamide (retention enhancer) at 0.1% by weight each.

They were added in amounts of 0.8% by weight, 20% by weight, and 0.03% by weight (relative to the pulp solid content), and were
P8209) was used to make paper sheets under the following conditions.

Parzo: Hardwood bleached sulfate pulp (LBKP) to
'o% Beatenness: 41. , Q+++l (JISP812
(Canadian standard freeness measuring device (No. 1)) Paper basis weight = 80 g/m2 Drying conditions = 110°C x 2 minutes (rotary dryer.

(manufactured by Kumagai Riki Kogyo) The size degree of the obtained paper sheets was measured by the Stekicht method in accordance with JIS P 8122. The results are shown in Table 1.

Examples 2 to 3 and Comparative Examples 1 to 7 The same process as in Example 1 was performed except that the type of cationic starch was changed.

The results are shown in Table 1.

Example 4 Commercially available substituted cyclic dicarboxylic acid-based sizing agent (neutral sizing agent Y) (manufactured by National Starch Co., Ltd., product name: Fylan, main component, mainly composed of an adduct of octade-9-maleic anhydride) After adding 5 parts by weight of an emulsifier (adduct of 7 ethylene nonyl ether: 10 moles of ethylene oxide) and 1000 parts by weight of water to 100 parts by weight of succinic anhydride, the mixture was mixed with a homomixer. A sizing emulsion was prepared by stirring for 5 minutes, and the treatment was carried out in the same manner as in Example 1, except that this sizing emulsion was used. The results are shown in Table 1.

Examples 5 to 6 and Comparative Examples 8 to 10 In Example 4, the same treatment as in Example 4 was performed except that the type of cationic starch was changed.

The results are shown in Table 1.

*1: After boiling at 95-100°C for 30 minutes, measure the viscosity of a 3% cationic starch aqueous solution using B-type viscosity (measurement temperature 50°C) *2: Indicates the degree of IS ionization of starch (glucose Shows the number of moles of substituents per mole of residue.
It was determined according to "Colloid Titration Method" (published by Nankodo). ) *3: Made by Nihon Shokuhin Kogyo ■, Neotac 115D *4: Obtained in Synthesis Example 1 *5: Obtained in Synthesis Example 2 *6: Made by Nippon Shokuhin Kogyo ■, Neotack 53 * 7:
tt, Neotac 30*8: tt, Neotack 130A*9:
tt, Neotac 330A*10: manufactured by Nippon Deka Chemical ■,
Excel HM* 11: // , Excel
l-3* 12: //, Excel 2 Patent Applicant Idemitsu Petrochemical Co., Ltd. Representative Patent Attorney Kubo 1) Fujibe Procedural Amendment (Spontaneous) June 4, 1980 Commissioner of the Patent Office Kazuo Wakasugi ■, Small case indication patent application No. 58-244326 2. Name of the invention Size composition 3. Person making the amendment Relationship to the case Patent applicant Idemitsu Petrochemical Co., Ltd. 4. Agent ■104 Address 1-1 Kyobashi, Chuo-ku, Tokyo No. 1o No. 5, Detailed explanation of the invention column 6 of the specification subject to amendment, contents of the amendment (1) "Made by Nihon Shokuhin Kogyo 91," on page 14, line 8 and line 11 of the specification. Corrected to ``Made by Food Chemical Industry 91.''

(2) Add the following sentence after line 17 on page 14.

[Example 7] Processing was carried out in the same manner as in Example 1 except that the type of cationic starch was changed.

The results are shown in Table 2.

Example 8 The same process as in Example 4 was carried out except that the type of cationic starch was changed.

The results are shown in Table 2.

Table 2 (1st page) Supplementary proceedings (voluntary) December 7, 1980 Manabu Shiga, Commissioner of the Japan Patent Office 1. Indication of the case Patent application 1982-244326 2. Name of the invention Size composition 3. U to make an amendment Relationship to the case Patent applicant Idemitsu Petrochemical Co., Ltd. 4, Agent ■ 104 Address 5, 1-1-1-1 Kyobashi, Chuo-ku, Tokyo Column 6 for detailed description of the invention in the specification subject to amendment , Details of amendment (1) r L HK P(
Laub 1lolz Kraft Pu1p) J
l-L B KP (L'aub 1+012111
eacl+ed Kraft Pu1p) Correct to j.

(2) “40°C” on page 9, line 11 of the same page is changed to “80°C”
Correct to.

(3) On page 10, line 5 of the same page, “carbon number 1L-18J is 1
Corrected to 14-20 due to carbon.

(4) Replacement with a boiling point of 150 to 240°C obtained by performing one reaction and distilling it under reduced pressure at a degree of vacuum of 1 ml 116. ” to B
1 stop.

(5) f-0, 1st line ■%-1 on the 3rd line from the 10th true
is corrected to ``rO, 15 double foot%''.

(6) "1000 parts by weight" in the 4th line of page 12 is r
Corrected to ``i o o o o heavy mouse section''.

(that's all)

Claims (1)

[Claims] 1. Ionic starch whose product of the viscosity (centipoise) of a 3% aqueous solution at 50°C and the degree of cationic substitution (number of moles of substituents per mole of glucose residue) is 6 to 14. and a neutral sizing agent.