JPS58132200A - Secondary stencil 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 second original paper using a special transparentizing agent.

The second original drawing paper referred to in the present invention refers to tracing paper used for design drafting and copying, copy paper, and also the second original drawing paper that is used for producing the second original drawing by a known method such as diazo method, silver halide method, electrophotography method, etc. This is a transparent record used to create. The properties required for Konera's second original drawing paper are: 1) It must be transparent; 2) The assembly strength, that is, tear resistance, folding resistance, and bursting resistance, must not be damaged during use by dogs. , 3) No bending or cranking, 4) Excellent dimensional stability, no curling, waving, etc., 5) Good ease of addition, correction, and erasing, 6) Transparency decreases during storage. For any purpose, there may be no yellowing or yellowing. Furthermore, when such a second original paper is used in a PPC copying machine, etc., it is necessary to ensure that 1) toner adhesion is good, and 2) toner correctability, that is, when erased with correction fluid, toner is 3) Can be completely removed and does not become opaque with correction fluid; 3) Does not generate a bad odor; 4)
) have good heat resistance, 5) do not cause transport defects due to double feeding or jams, 6) do not cause charging problems, and 7) do not contaminate the fixing roller. No second original drawing paper has been obtained that fully satisfies the above-mentioned required characteristics.

Conventional second original paper includes (a) tracing paper made by beating cellulose-based natural pulp to a highly viscous state, or tracing paper further treated with a polymeric substance; (b) Paper that is relatively opaque compared to (a) tracing paper and is impregnated with oils, plasticizers, liquid paraffin, etc. ()・) Plastic film is used as a base material and various surface treatments are applied to it. and (d) those made by mixing thermoplastic synthetic resin-based synthetic pulp with cellulose-based natural pulp and making it transparent by heat treatment.

Among these conventional second original drawing papers, the second original drawing paper obtained by method (a) is the most widely used, but this is extremely sensitive to humidity and causes curls, waves, etc. Dimensional stability is poor. Furthermore, it is inferior in paper strength such as water resistance and tear resistance. On the other hand, the second original paper (b) has slightly better water resistance and dimensional stability, but migration of the transparency agent occurs during long-term storage or due to the heat inside the copying machine, which can cause image bleeding. Cause. In addition, they generally have poor writability and also have drawbacks such as easy cracking at folds. Furthermore, it is less transparent than the paper in (a). Although the second original drawing paper created by the method (c) is relatively superior in transparency, dimensional stability, and strength, it has the drawbacks of poor writability and workability during liquid application, and high cost. be. Furthermore, although the second original drawing paper (d) has good dimensional stability, the distribution of synthetic pulp and natural pulp is uneven, and it is difficult to achieve uniform transparency, with scattered opaque spots and History also has its drawbacks in terms of ease of writing and cost.

Generally, to make paper transparent, as is well known, voids in the paper layer are filled with a clarifying agent having a refractive index similar to that of cellulose fibers. However, when a liquid or low-melting solid substance is used as a clarifying agent, many problems such as those mentioned in (o) above occur. In some cases, the penetration of the transparentizing agent into the inside of the paper layer is incomplete, making it difficult to achieve uniform high transparency processing.

Therefore, research is currently being conducted on clarifying agents that have relatively low molecular weight and that can be cured by catalysts, heating, ultraviolet irradiation, or other means after sufficiently penetrating into the interior of a base material such as paper. Therefore, several reactive resins, oligomers, or monomers have been investigated.As such force-transparent agents, for example, thermosetting resins such as phenolic resins, urea resins, melamine resins, and alkyd resins can be used alone. or a combination thereof, but in this case, both have a slow curing speed,
Although it is possible to increase the curing speed somewhat by increasing the curing temperature and adding an acid catalyst, this is not preferable because it causes deterioration of the base material by making the curing conditions harsher. Furthermore, the transparent paper obtained by using the thermosetting resin becomes hard, the paper strength decreases, and it becomes easy to tear, or it becomes easy to generate odor when heated.

Further, as another method, for example, an example in which an oligomer having an incyanate group is used as a clarifying agent as disclosed in JP-A-52-46113, or JP-A-52-46113,
-Using a clarifying agent that is a combination of polyisocyanate and polyester polyol as disclosed in Publication No. 3'6367; Polyurethane and other polymers are produced in the lower layer by using the resin, but in either case, yellowing is relatively easy to occur, and curling occurs due to high moisture absorption, so it is not necessarily suitable for use in RPC copying machines. .

The purpose of the present invention is to provide a second original drawing paper that solves the above-mentioned conventional drawbacks, and in particular, by examining various clarifying agents, tear resistance, burst resistance, etc. A second original drawing paper that has excellent paper strength, fold cracking, correctability, and erasability, excellent dimensional stability, and resistance to curling and waviness, and is also suitable for use in various types of copying machines such as PPC copying. O 1J [1, the present invention is directed to an addition reaction using diisocyanate or polyisocyanate as the first component, having 2 to 8 hydroxyl groups at the terminal, and propylene oxide or ethylene oxide alone or in combination. The second original paper is characterized in that the polyether polyol obtained by this process is used as the second component, and the alkanol amino resin is used as the third component, and these are cured by a polymerization reaction on the surface of the base material. be.

As the diisocyanate or polyisocyanate that is the first component, commonly used diisocyanate compounds such as tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, dicyclohexyl diisocyanate, lysine diisocyanate, etc. However, from the viewpoint of toxicity and storage stability, for example, the product names Desmodur L1 Coronate L, Takenate-DIO2, Dll
Polyhydric alcohol adducts of diisocyanates such as ON, or desmodule N, fsmodule TT
, fsmodur II, desmodur HL, Coronate 2030, Suprasenok 3240, and other diisocyanate polymers are preferably used. Furthermore, as a so-called blocked isocyanate in which an adduct is formed using an active hydrogen compound such as phenol, a primary alcohol, or caprolactam, for example, products such as Coronet (trade name) AP, f Smodul AP staple, Burnock D-91, etc. may be used. You can also do it. In addition, if there is a particular restriction in terms of yellowing, hexamethylene diisocyanate, xylene diisocyanate, or a polymer thereof that does not cause yellowing, such as Desmodur N, may be selected and used.

Furthermore, aliphatic diisocyanates have weaker reactivity than aromatic diisocyanates, but this should be taken into consideration when selecting them. In particular, in acid catalyst addition systems, depending on the amount of acid catalyst added, for example, when an aromatic polyvalent isocyanate such as Desmodur L is used, thickening may easily occur and coloration may occur due to complex formation. It may not be able to withstand long use.

The second component has 2 to 8 hydroxyl groups at the terminal, and propylene oxide or ethylene oxide is used alone or in combination,
As is well known, the polyether polyol obtained by the addition reaction produces a polymeric polyurethane having a chain or network structure by reacting with the incyanate, and by reacting with the alkanolamino resin described below, a network-like polyurethane is produced. Although it does not produce a structure, those commonly used as raw materials for urethane resins can be used.

Examples of polyether polyols having 2 to 8 hydroxyl groups at the terminals include propylene glycol, trimethylolprono(n), glycerin, pentaene, etc.
Aliphatic so-called star-shaped polymers such as J, α-methyl glucoside, sorbitol, and sucrose may be used, and aromatic polyphenols such as bisphenol A may also be used. These polyether polyols have compatibility with solvents depending on the polyol skeleton, the type of ring-opening polymerization reactant, that is, the 3-membered ring compound, and the number of added moles, and mainly due to the reaction with the second component, diisocyanate or polyincyanate. In order to change the flexibility etc. of the urethane polymer produced, it is necessary to take these into consideration when selecting.

Examples of the third component, alkanol-amino resin, are:
As the 7-mino resin, urea resin, melamine resin, guanamine resin, etc. can be used alone or in combination. The modified alkanol can be used from lower alcohols such as methanol to higher alcohols such as Octatool, but it is difficult to use in terms of permeability to paper, curing properties, stability, compatibility, flexibility, and hardness. From the viewpoint of moisture resistance, price, etc., alkanols having 3 to 5 carbon atoms are preferred. Next, the degree of methylolation and degree of methylation of the amino resin may be any degree as long as there are no problems with compatibility, curability, stability, etc.; The degree of methylolation is preferably 3 to 5, the degree of etherification is 1 to 3, and in the case of urea resins and guanamine resins, the degree of methylolation is preferably 1 to 3, and the degree of etherification is approximately 0.5 to 2. In addition, the molecular weight is 1000 from the point of permeability into paper.
It is desirable that it be below that level.

The reason why amine resin is used in the present invention is that this resin has superior curability and stability compared to thermosetting resins such as phenolic resins, epoxy resins, and unsaturated polyester resins. This is not only because it is easy to use, but also because the resin is light in color, has good weather resistance and yellowing resistance, and can provide transparency with excellent near-ultraviolet light transmittance. By appropriately selecting the composition of the amine resin and its blending ratio with respect to the second component, polythenyl-terpolyol, it is possible to freely change the composition from highly flexible to hard and chewy. In order to prevent blocking of the curing agent, migration, and blurring of the image, and to improve solvent resistance, writability, and paper strength, it is necessary to mix the curing agent within a certain range, as described below.

Regarding the blending amounts of each of the above components, diisocyanate or polyisocyanate as the first component and propylene oxide or ethylene oxide having 2 to 8 hydroxyl groups at the terminal as the second component are used alone or in combination to undergo an addition reaction. The blending ratio of the polyether polyol obtained by this method varies depending on the use and the type of clarifying agent, but the first component should be at least 2 parts by weight per 100 parts by weight of the second component,
Preferably, it is used in an amount of 5 parts by weight or more and 50 parts by weight or less. The effect of adding the first component is as follows:
(1) Good imprintability and drying properties of water-based inks and water-based stamps, (ii) Good resistance to creases, (iii)
Paper strength, especially folding strength, tear resistance, and bursting resistance are strong, and paper strength loss after heating storage is improved.(1v) It is easy to obtain transparent paper with excellent appearance without surface gloss. It can exhibit superior features compared to a clarifying agent consisting of a combination of only two components and a third component.

If the first component is less than 2 parts by weight, such excellent features cannot be exhibited. If the first component is more than 50 parts by weight, the incyanate active group will rapidly accelerate the polymerization reaction by the acid catalyst described below, causing problems with the bot life of the liquid due to foaming, thickening, etc. Not only is manufacturing difficult, but the resulting second original paper is also prone to curling and waviness, and is susceptible to conveyance defects during copying, making it unusable for PPC copying machines.

The amount of the alkanol amino resin component, which is the third component, is 20 parts by weight or more, preferably 25 parts by weight or more, based on 100 parts by weight of the polyether polyol, which is the second component.
It is desirable to use it in an amount of 0.00 parts by weight or less. If it is less than 20 parts by weight, the curing reaction will not be completed even if the amount of acid catalyst is increased, and migration of the clarifying agent will occur, resulting in a decrease in solvent resistance. In addition, an increase in the second component makes the resulting second original paper hard and chewy, and a moderate amount (30 to 40 parts by weight) improves whitening on folding and prevents curls and waves caused by environmental changes. can be reduced.

However, if the amount is more than 106 parts by weight, the second original paper becomes easily torn and at the same time generates an odor, making it difficult to use it as a second original paper for a PPC copying machine, for example.

The curing reaction of the first component, second component, and third component varies depending on the type of clarifying agent, the amount of acid catalyst, and the drying conditions and heat treatment conditions after applying the clarifying agent liquid to the substrate, but Does not require harsh curing conditions like a clarifying agent, and can be cured at most 12
Heat treatment at 0° C. for 1 to 2 minutes or an equivalent heat treatment is sufficient, and there is no need to damage the base material. In particular, by using the first component, depending on the amount of acid catalyst and the amount of clarifying agent, curing can be achieved even if left alone for 1 to 5 days at room temperature.

Examples of the acid catalyst include carboxylic acid esters such as p-t/leenesulfonic acid, motubutyl phosphate, or dimethyl oxalate, and acid anhydrides such as maleic anhydride and phthalic anhydride.

These acid catalysts may be impregnated into the substrate in advance, but more preferably they are contained in the following solvent together with the above-mentioned clarifying agent and then adhered to the substrate. The amount of the acid catalyst to be used varies depending on the solvent used, but when using a polar solvent such as water or alcohol, it is preferably 10 parts by weight or more and 35 parts by weight or less based on 100 parts by weight of the second component. . When the solvent is a nonpolar solvent such as an aromatic hydrocarbon, 7 parts by weight or more and 25 parts by weight per 100 parts by weight of the second component.
It is desirable that the content be less than parts by weight. Insufficient curing causes migration of the clarifying agent, which not only impairs image quality due to image bleeding, but also causes water-based ink and the like to bleed. Therefore, it is necessary to completely cure the resin, but if the amount of the acid catalyst is less than the above range, the curing will not be completed unless the heating temperature during curing is 150° C. or higher. However, heating above 150° C. significantly deteriorates the paper strength of the base material. If the amount of acid catalyst used exceeds the above usage range, the stability of the clarifying agent solution will be significantly impaired and the quality will deteriorate, or the excess catalyst will make the original plate brittle or yellow after it has adhered to the substrate. This will deteriorate storage stability, such as deterioration.

Examples of organic solvents that dissolve the above-mentioned clarifying agent include commonly used ketones such as methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as benzene and toluene, etc. alone or in combination. However, especially in the case of the present invention's clarifying agent, significant differences can be seen in the paper strength, surface gloss, and viscosity change of the clarifying agent liquid of the resulting second original paper depending on the polarity of the solvent used. It was found as follows, that when alcohols, which are polar solvents, are used, even though they contain active groups that are reactive with incyanate groups,
The viscosity change of the clarifying agent liquid over time is rather small and stable compared to aromatic hydrocarbons such as toluene and ketones such as methyl in butyl ketone, so it can be used, but the paper strength of the resulting second original paper The strength, especially the tear resistance and bursting resistance, is inferior to the latter, and if it is hardened and dried with a dryer,
The surface becomes glossy, which not only spoils the appearance but also
This is not very preferable because it causes problems in the water-based ink addition property and the water-based stamp printing property.

On the other hand, when a nonpolar solvent such as toluene is used, the viscosity change over time of the clarifying agent liquid is slightly larger than that of alcohols, but there is no problem in actual use, and there is a decrease in paper strength.
There is no shine and it is elegant. When ketones such as methyl isobutyl ketone are used, alcohols and aromatic hydrocarbons exhibit intermediate behavior.

Therefore, it is desirable to select a mixed solvent system in which a polar solvent and a nonpolar solvent are appropriately mixed as the solvent system in which all of the clarifying agent is dissolved.

Next, regarding the method for preparing the clarifying agent, since it contains an incyanate component and an acid catalyst, it is preferable to prepare it in the following order. That is, the polyol as the second component and the alkanol amino resin as the third component are first mixed with a solvent, then an acid catalyst is added, and after stirring,
Add the first ingredient, incyanate.1o If,
If the isocyanate and the acid catalyst are directly mixed, a gelatinous precipitate will quickly occur. Furthermore, if the acid catalyst or incyanate is added to the second component polyol without mixing the third component alkanol amino resin, a sudden exothermic reaction may occur, which is dangerous. Therefore, a mixed system of polyol, alkanol amino resin, and solvent is first prepared, and then an acid catalyst and
A suitable method is to add incyanate while stirring slowly.

In addition to the above components, auxiliary agents such as plasticizers, penetration aids, antistatic agents, fillers, colorants, or lubricants may be used as necessary. Also, after the transparency process, a second coating with resin etc. may be applied to one or both sides of the second original paper.
As the base material used in the present invention, any known material such as paper, woven fabric-1 non-woven fabric, etc. can be used, and examples include high-quality paper with a basis weight of 20 to 100 f/- for good shearing.

To attach the transparentizing agent to the base material, it is recommended to impregnate it using a simple dip squeeze method, or apply it using an air knife method, a glass doctor method, a wire bar method, a roll coater method, etc., to make it transparent. After applying the agent solution, it is sufficient to simply dry it by removing the solvent with cold air or hot air of 50° C. or less, and there is no need to heat it to a particularly high temperature.

The amount of the clarifying agent applied is 5 to 80 inches, especially 1 inch, of the substrate after drying.
It is preferable to set it to 0 to 50%. dry for 50
If hot air exceeding ℃ is used, the curing reaction will proceed before the transparentizing agent has sufficiently and uniformly penetrated into the base material, and the surface of the resulting second original paper will become extremely glossy, reducing the ease of addition and transparency. So I don't like it. After drying, it is usually left to stand at room temperature to ripen and then harden.

Curing can be achieved by simply leaving it for 1 to 5 days depending on the clarifying agent and acid catalyst used, but usually it is cured at 120°C for at most 1 day using a dryer in the coating machine or an appropriate heating means.
The material may be heated for ~2 minutes, or an equivalent heat treatment may be performed.

If the curing is carried out under pressure, a second original paper with particularly excellent transparency can be obtained. Further, supercalender treatment may be performed after curing.

As mentioned above, the above-mentioned transparentizing agent of the present invention has a relatively low molecular weight, so it has good permeability into the inside of the base material, makes the base material uniformly transparent, and does not give the surface gloss unlike conventional ones. ,
It can have an appearance similar to tracing paper. By curing the clarifying agent, there is no need to worry about migration of the clarifying agent or image blurring, and it has excellent dimensional stability, heat resistance, and toner correctability, as well as ease of writing with water-based inks, and paper strength. It has excellent properties such as high strength and no whitening of creases.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 A mixed pulp consisting of softwood pulp IO part and hardwood pulp part 90 part was prepared using Canadian Standard Freeness 35.
The paper was beaten to 0 cc to produce base paper with a basis weight of 5527. This base paper was impregnated with the following clarifying agent liquid, excess liquid was removed through a wire bar, and the paper was dried at 40° C. for 1,200 minutes and rolled up.

Clarifying agent liquid first component ° Trade name Desmodur N (manufactured by Bayer AG) 20 parts by weight Second component: p, o, addition type polyether diol (Uniol D-400 manufactured by Nippon Oil & Fats) 90 parts by weight Third component: Hexamethoxymethylolmelamine (Cynol 303 manufactured by Mitsui Toatsu) 40 parts by weight W: p-toluenesulfonic acid (trade name DR-50)
[Solid content 60%] manufactured by Tokushima Essential Oil Co., Ltd.) 15 parts by weight Solvent: 80 parts by weight of toluene 10 parts by weight of sweetened cellosolve acetate 10 parts by weight Then, after leaving to mature for 3 days, heat treatment was performed at 110°C for 1 minute and 30 seconds. , adhesion t 16 ? /rr? , opacity 38%, folding durability MD 100 times or more, bursting degree 3.4K
A strong second original drawing paper with a p/cJz tear degree CD35.2f was obtained. This second original drawing paper was excellent in terms of dimensional stability, toner correction property, addition property with water-based ink, etc., and crease whitening. The test method is opacity (JIS P 813
8), folding resistance (JISP 8115'), rupture degree (
JIS P 8112), tear degree (JIS P 81)
16).

Example 2 The base paper obtained in Example 1 was added with the trade name Desmosil N (manufactured by Bayer AG) as the first component, and P, 0.5% as the second component. What type 1 polyether triol (UNIOL TG-40
0 Nippon Oil & Fats Co., Ltd.), hexamethoxypamethylolmelamine (Cymel 301 Mitsui Toatsu Co., Ltd.) as the third component, p-toluenesulfonic acid as an acid catalyst (DR50a Shima M Oil Co., Ltd.), and toluene (solid content concentration). 5
3%) at the ratio (parts by weight) shown in the table, dry adhesion sensitivity 16~
l 7 f/lr? The physical properties of the obtained second original drawing paper are shown in the table below.

As shown in the triα table, as the first component, isocyanate, is added, the paper strength becomes stronger, the paper does not tear during handling, and the whitening of folds and the ease of adding water-based inks are also improved. However, if the third component, alkanol amino resin, is added more than necessary, the tear strength will decrease.
It can be seen that crease whitening also occurs more easily.

Example 3 A mixed pulp consisting of 20% softwood pulp and 80 pieces of hardwood pulp was prepared using Canadian Standard Freeness 4.
Beating to 00 cc and basis weight 56? /rr? The original paper was made. This base paper was impregnated with the following clarifying agent liquid, excess liquid was removed through a wire bar, and the paper was dried for 2 minutes at room temperature and rolled up.

Clarifying agent liquid first component' Trade name Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) 30 parts by weight Second component: E, O, addition type polyether diol (Uniol DA-400 manufactured by Nippon Oil & Fats) 90 parts by weight Third component: Methyl ethyl mixed alkylation type methylolmelamine (Cymel 1116 manufactured by Mitsui Toatsu) 60 parts by weight Acid catalyst: p-toluenesulfonic acid (trade name DR-50 manufactured by Tokushima Seisei) 15 parts by weight Solvent: 85 parts by weight of methiisobutyl ketone 20 parts by weight of cellosolve acetate Then, after being left to mature for 2 days, heat treatment was performed at 120°C for 1 minute, resulting in a coating weight of 18? /rn", 'Opacity 4
1%, folding durability MDl'000 times or more, bursting strength 3.8k
A strong second original drawing paper having a g/crl z tear degree CD39.01i' was obtained. This second original paper also had excellent performance as described in Example 1.

Example 4 The base paper obtained in Example 1 was immersed in the following clarifying agent liquid for 5 seconds using a dip squeeze method, passed between two pressure rolls to remove excess liquid, and then wound up.

Clarifying agent liquid 1st component: Trade name Desmodur N (manufactured by Bayer AG) 30 parts by weight 2nd component: p, o, addition/E, 0. Addition type polyether diol (Uniol DAB-800 manufactured by NOF Corporation) 90 parts by weight Third component: Hexamethoxymethylolmelamine (Cymel 303 manufactured by Mitsui Toatsu) 40 parts by weight Acid catalyst: p-) Luenesulfonic acid (trade name DR- 50 Tokushima Essential Oil Tokushima Essential Oil Type Quantity Part Solvent: 100 parts by weight of toluene Then, after leaving to mature for 3 days, 120°C.

Heat treatment was performed for 1 minute, and the amount of adhesion was 18? /rr? , opacity 43%, folding dust MD 100 times or more, bursting degree 3.2
A tough second original paper with kq/cl and tear dust CD of 33.79 was obtained. This second original paper also had excellent performance as described in Actual KQ Example 1.

Example 5 The base paper obtained in Example 3 was immersed in the following clarifying agent solution for 5 seconds using a dip squeeze method, the excess liquid was removed by passing it between two pressure rolls, and the paper was dried with cold air for 2 minutes. I wound it up.

Clarifying agent liquid first component: Product name LDI-A100 (manufactured by Toshisha) 1
5 parts by weight Second component: 'p, o, addition type polyether hexanol (Sannisox 5P-750 manufactured by Sanyo Kasei) 90 M parts Third component: Hexamethoxymethylolmelamine (Cymel 301 manufactured by Mitsui Toatsu) 30 parts by weight acid catalyst : p-Toluenesulfonic acid (trade name: DR-50 Tokushima essential oil type) Solvent: 50 parts by weight of xylene 1.40 parts by weight of methanol Then, after leaving to mature for 3 days, heat treatment at 130°C for 1 minute. A strong second original paper with a coating weight of 16 mm, an opacity of 40 inches, a dust resistance MD of 100 times or more, and a bursting degree of 3.5 kg/crI% and a tear degree of CD 35.6F was obtained. The original paper also had excellent performance as described in Example 1.

Patent applicant Ricoh Co., Ltd. Representative Patent Attorney Hidetake Komatsu

Claims (1)

[Claims] 1. The first component is diisocyanate or polyisocyanate, and the second component is polyether polyol, which has 2 to 8 hydroxyl groups at the terminal and is obtained by addition reaction with propylene oxide or ethylene oxide alone or in combination.
A second original drawing paper characterized in that it contains an alkanol amino resin as a third component and is cured by a polymerization reaction on the surface of a base material.