JPS62162585A - Recording material - Google Patents

Abstract

PURPOSE:To contrive higher ink absorptivity, better dot shape, higher color properties and higher image density, by specifying the covering ratio of a pigment and the peak height at a predetermined wavelength in a power spectrum with varying thickness, and providing a recording surface with a specified compound. CONSTITUTION:A recording material shown the most excellent ink absorptivity and excellent dot shape when the covering ratio of a pigment is set to be 5-80%. When the peak height at a wavelength of 10mm in a power spectrum with varying thickness is set to be not more than 1.5 times that at a wavelength of 5mm, more excellent ink absorptivity, dot shape, color properties or the like can be obtained irrespective of changes in the kind of the recording material. Further, when a compound capable of causing a water-soluble dye contained in a water base ink applied to immediately separate out at the surface of the recording material is added to the surface, a high image density can be obtained. The compound having such an action is particularly preferably an alkali metal halide or an alkaline earth metal halide.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a recording material, and more particularly to a recording material for inkjet recording for recording with aqueous ink.

(Prior Art) Inkjet recording methods include various ink (recording liquid) ejection methods, such as an electrostatic suction method, a method that applies mechanical vibration or displacement to the ink using a piezoelectric element, and a method that heats the ink to foam it. Recording is performed by using a method that uses the pressure to generate and fly ink droplets, and some or all of them adhere to a recording material such as paper, but it generates little noise and It is attracting attention as a recording method that allows high-speed printing and multicolor printing.

As the recording material used in this inkjet recording method, commercially available heavy to medium-quality paper generally called brain paper and recording material called inkjet recording paper have been used.

Although commercially available medium-quality papers have excellent writing properties and printability, they have the following drawbacks when subjected to inkjet recording.

(1) During or after inkjet recording, if a part of the recording device or your finger touches the recording section, the ink will not be received quickly and the ink that has not been accepted will rub off.
Staining occurs and image quality is significantly degraded. Furthermore, the records may become illegible.

(2) After the ink adheres to the recording material, feathering occurs from the dots, resulting in dots with extremely low roundness. For this reason, the dot shape is poor and a clear image cannot be obtained.

On the other hand, as the performance of inkjet recording devices improves and spreads, various recording materials have been devised as recording materials for inkjet recording in order to obtain high-resolution, high-quality recorded images (for example, JP-A-59 -35977, JP 58-132586, JP 52-74340
(see publication).

However, JP-A-59-35977 and JP-A-58
The recording materials described in Japanese Patent No. 132586 and the like are coated papers for inkjet recording that have high ink absorbency and excellent color development, but these recording materials have the following drawbacks.

(3) When writing on a recording material with a writing instrument such as a pencil or a fountain pen, the ink receiving layer is scratched and the writing cannot be done properly.

(4) When ink-end recording is performed on a recording material, mechanical friction between the recording material and the paper feeding part of the recording device causes
The coating layer peels off, so-called powder falling, which contaminates the recording device. In particular, if the fallen ink receiving layer adheres to the head of an inkjet recording device, it may cause clogging of the nozzles of the head.

Furthermore, the inkjet recording paper described in Japanese Patent Application Laid-open No. 52-74340 and the like has the following drawbacks when inkjet recording is performed.

(5) Low dot density.

(6) The first side of the dot b tends to be blurred, making it impossible to obtain a clear image.

(7) A phenomenon in which ink bleeds onto the back side of the recording surface, so-called strike-through, occurs.

Conventional recording materials have the above-mentioned drawbacks, and the current situation is that no recording material that solves all of these drawbacks has been obtained.

Therefore, an object of the present invention is to solve the above-mentioned drawbacks, and to provide a high-performance inkjet that has rapid ink absorption, excellent dot shape, and particularly good color properties and forms clear images with high image density. The object of the present invention is to provide a recording material for recording.

(Disclosure of the Invention) That is, the present invention provides a recording material whose main component is fiber, in which the percentage of the area covered by the pigment on the recording surface of the recording material (hereinafter referred to as pigment coverage) is 5 to 80%. Yes, the peak height at a wavelength of 10 m+s in the power spectrum of the thickness variation of the recording material is within 1.5 times the peak height at a wavelength of 5 ml, and when ink containing a water-soluble dye is attached, the water-soluble dye This recording material is characterized in that a compound that causes the precipitation of a dye is applied to the recording surface.

Next, to explain the present invention in more detail, the present inventor has conducted intensive research to obtain a recording material for inkjet recording using water-based ink, which solves the drawbacks of the prior art. When the recording material as the main component has specific surface physical property values and its recording surface contains a specific compound, it can be used as a recording material for inkjet recording with excellent ink absorption and prevents ink bleeding and feathering. It was discovered that a recorded image with excellent dot shape, particularly good color properties, high density, and high resolution was obtained without the occurrence of rings.

That is, there has been no clear explanation regarding the behavior of a liquid, for example, an aqueous ink, permeating into a recording material mainly composed of fibers such as paper.

For example, the penetration of a liquid into a porous object can be explained to some extent by the Lucas-Washburn equation, but this equation requires that the flow in a pipe is laminar, that the acceleration of the flow velocity is very small, etc. Under the preconditions,
Hagen-Poiseuil
Since it is a development of the above equation, the range in which the Lukas-Worsbahn equation can be applied to actual phenomena is quite limited.1 For example, regarding the penetration of non-aqueous liquids, it is important to limit the properties of the recording material. This proves that it can be applied. However, for aqueous liquids such as water-based inks used in inkjet recording, the surface properties of the recording material and the liquid flow path due to swelling change over time as the liquid penetrates, so the Lucal-Werschburn formula is directly applied. Can not.

On the other hand, the factors of the recording material that control the penetration of liquid into the recording material include the solid surface tension of the recording material, wettability, adsorption capacity, pore size, geometric structure such as shape distribution, etc. etc., but it is currently impossible to strictly measure these controlling factors.

For example, it is possible to measure the solid surface tension of individual substances that make up the recording material, but it is not possible to precisely measure the surface tension of a recording material such as paper, which is a complex mixture of various substances. are various materials that form the recording material, mainly fibers,
Since various substances such as pigments and binders are present non-uniformly, it is impossible to measure them uniformly. Furthermore, it is impossible to specifically measure the wettability and liquid adsorption capacity of the recording material.

Although one example has been given above, regarding various other physical properties as well, it is extremely difficult to accurately measure the behavior of liquid, particularly aqueous liquid, permeating into the recording material.

The present inventor has conducted various studies regarding the relationship between these recording materials and the water-based inks used for recording, regarding recording materials whose main component is fibers, that is, paper thread recording materials, especially recording materials for inkjet recording. As a result, the permeability of water-based ink to paper thread recording material depends on the fibers and fillers used (
(pigment), binder, sizing agent, antifoaming agent, etc., and even if the recording material is made of the same material, the physical properties of the recording material relative to water-based ink will vary greatly depending on the state of aggregation of these materials. However, even if these materials and combinations vary, the absorbency of water-based ink is most affected by the presence of pigments that make up the recording material, especially when the pigment coverage is 5 to 80%. I have learned that sometimes the best thing is.

That is, when the pigment coverage exceeds 80%, the amount of binder relative to the pigment is insufficient, resulting in powder falling during recording and poor writability (recordability).

In addition, if the amount of binder used is increased to solve these drawbacks, the wettability with water-based ink may decrease,
The number of pores through which the aqueous ink penetrates is reduced, making it impossible to obtain sufficient ink absorbency.

In addition, if the pigment coverage is less than 5%, powder fall-off will not occur during recording, but many pores in the recording material will not be filled with pigment, and the liquid will be absorbed into the pores. This is undesirable because the water-based ink may become trapped by the pigment, pores that are not filled with pigment may inhibit the penetration of the water-based ink, or the penetration of the water-based ink may become uneven, resulting in bleeding or feathering of the water-based ink.

Therefore, the recording material of the present invention has a pigment coverage of 5 to 80.
%, and exhibits the best ink absorbency and the best dot shape within this range.

However, even with recording materials having such a pigment coverage rate, there may be cases where the ink absorption, dot shape, and color properties are insufficient depending on the type of paper, and the present inventor is conducting further research on these cases. As a result, it was discovered that the above problem mainly occurs due to variations in the thickness of the recording material, and the wavelength 1OII1 of the power spectrum of the thickness variation
The peak height of 1 is 1.5 of the peak height of wavelength 5a+m.
It has been found that when the difference is within twice as much, even better ink absorbency, dot shape, color properties, etc. are exhibited despite changes in the type of recording material.

That is, the pigment coverage of the recording material is 5 to 80 as described above.
%, the wavelength of the power spectrum of thickness variation is 10
If the peak height of the +s layer exceeds 1.5 times the peak height of wavelength 51, sufficient ink absorption, excellent dot shape, and excellent color properties cannot be obtained. Therefore, this point is the second feature of the present invention.

The power spectrum of such thickness fluctuations can be obtained by taking a cross-sectional photograph of the recording material using an SEM or an optical microscope, and measuring the thickness of the recording material using a graphic digitizer. , Blackma
This can be determined using the n-duke method or the like.

Further, the power spectrum of the thickness variation of the recording material can be adjusted by the paper making method, valve processing, and various additives.

The recording material of the present invention having the first and second features as described above has excellent ink absorbency, dot shape, and high color properties even if the composition of the recording material varies to some extent. However, since the water-soluble dye in the water-based ink sufficiently penetrates into the inside of the recording material, the image density on the surface cannot necessarily be said to be sufficient.

In order to solve these problems, the present inventor conducted research to obtain a recording material that provides an image with high density as well as excellent ink absorption, excellent dot shape, and high color quality. By adding a specific compound, that is, a compound that causes the water-soluble dye in the applied water-based ink to immediately precipitate on the surface of the recording material, the liquid medium in the applied water-based ink can penetrate into the inside of the recording material. Although quickly absorbed, the water-soluble dye in the water-based ink was found to precipitate immediately on the surface of the recording material, giving a high image density. Therefore, this point is the third feature of the present invention.

Preferred compounds that have the above effects include:
As water-soluble dyes in water-based inks, acid dyes and direct dyes are often used, so alkali metals, alkaline earth metals, other metals such as lithium, potassium, sodium, magnesium, calcium, etc.
Water-soluble metal salts such as aluminium, strontium, manganese, etc., such as halides, carbonates, sulfates, sulfites, nitrates, etc., and especially halides of alkali metals and alkaline earth metals, can be used as water-soluble dyes in aqueous inks. This is preferable because the water-soluble dye can be immediately precipitated without changing the hue of the dye.

Among water-soluble metal salts, some are acidic, and these salts can unevenly dissolve the sizing agent in the recording material, making the water-based ink permeate unevenly, damaging the dot shape, and even damaging the dot shape. This is not very preferable because it changes the hue of the water-soluble dye and causes the water-soluble dye to precipitate. Therefore, among the above-mentioned water-soluble metal salts, compounds exhibiting a pH of 6 or more as an aqueous solution are preferred.

Other preferred compounds include low molecular weight organic compounds such as organic amines and organic ammonium salts, such as non-volatile organic amines and organic ammonium salts; polyallylamine salts;
Examples include basic oligomers or polymers such as polyamine sulfonic acid quaternary ammonium salt, polyaminopolyamine/epichlorohydrin reaction product, and dicyandiamide/formalin condensate.

Suitable organic compounds include oligomers or polymers having primary to tertiary 7-mino groups as described above, or quaternized products thereof, and particularly preferred organic compounds having the following general formula (
Examples include basic oligomers or polymers represented by I) to (m).

(R1, R2, and R3 in the above formula are a hydrogen atom, an alkyl group that may have a substituent, and an alkenyl group.

alkanol) represents an integer from allylalkylnyl to 10. ) (II) -(:CH2-CH)n
-Author H2 (In the above formula, R1, R2.R3 are hydrogen atoms, alkyl groups that may have substituents, alkenyl groups, alkanolkenyl groups, X is acid groups, n is 5 to 100,000 (In the above formula, R1 and R2 are a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group, an alkanol group, an allylalkyl group, an allylalkenyl group, X is an acid group, n represents an integer from 5 to 100,000.) Compounds represented by general formulas (I) to (m) include, for example, Nalpoly-607 (manufactured by Nalco Chemical), Polyfix 601 (Showa Kobunshi type), Percoll 1697 ( Allied Colloid Acid), CatFlohe (Carbo7 Car
manufactured by p), PAS (manufactured by Nittobo), Neofix RPD
It is commercially available under trade names such as (NICCA Chemical Type) and can be suitably used in the present invention.

The recording material of the present invention having the above-mentioned characteristics can be obtained according to a conventionally known paper manufacturing method and/or paper post-processing method. For example, the fiber used as the main component may be wood pulp. Synthetic pulp, synthetic fibers, glass fibers, etc. are used in combination depending on the purpose, and necessary additives such as pigments as fillers, sizing agents, various binders, dispersants, and waterproofing agents are added to these materials. Obtained by papermaking. Furthermore, various physical properties of the paper can be adjusted by subjecting the obtained paper to surface treatment such as surface size treatment.

Preferred pigments for coating the surface of the recording material include:
For example, silica, clay, talc, kaolin, diatomaceous, calcium carbonate, calcium sulfate, satin white,
Aluminum silicate, alumina, zeolite, etc. are used, and particularly preferred ones have a particle size of 0.05.
pm to 50 pLm, more preferably 0, 1 gm
~20 ILm. If the particle size is too large, the degree of bleeding of the aqueous ink in the horizontal direction of the recording material becomes uneven, which is not preferable.

The pigment coverage of the recording material of the present invention is 5 to 80% as described above.
In order to adjust the coverage, the pigment used during paper making should be used at a ratio of about 5 to 50 parts by weight per 100 parts by weight of fiber, which is the main component. It can also be adjusted by post-treatment with a coating liquid containing pigments and the like.

In addition, the wavelength of the power spectrum of the thickness variation obtained is 10 m.
The peak height of m is the peak height of wavelength 5mm.
In order to adjust L to 5 times or less, paper-making conditions may be set in a way that improves the paper formation, such as by using additives such as surfactants or by lowering the paper-making density.

In addition, as a method of applying compounds that precipitate water-soluble dyes to the surface of the recording material, the above-mentioned compounds may be added at the time of paper making, or these compounds may be added to the surface of the recording material by coating containing these compounds. It is also possible to prepare a chemical solution and apply it to the surface of the paper after paper making by any method such as a size press method or a spray coating method. In any case, these compounds may be present on the recording surface of the recording material. For example, if added internally during paper making, approximately 0.1 to 10 g/m
It is preferable to add it internally at a ratio of 0.1 to 10 g/m', and when it is later applied to the surface, it is preferably applied at a ratio of about 0.1 to 10 g/m'. concentration can be achieved.

The recording material of the present invention as described above can be used for fountain pens, felt-tip pens,
It is suitable not only for general writing instruments such as ballpoint pens that use water-based ink, but also as a recording material for ink-end recording that uses water-based ink, and has the following effects.

(1) Because the water-based ink is highly absorbent, after the ink is applied, it immediately becomes the same state as drying, and even if parts of the recording device or fingers are attached, it may contaminate them or the recorded image may become dirty. There is no.

(2) When used for inkjet recording, the above (
In addition to the effect of 1), the ink dots are nearly perfect circles and have a high concentration, causing excessive bleeding of the ink dots.

Since feathering does not occur from dots, clear and high-resolution images can be formed.

(3) When a compound that precipitates the water-soluble dye is added to the coating layer of coated paper, the strength of the coating layer increases, and the coating layer does not scrape off during writing or inkjet recording, resulting in an excellent It is possible to record a very high-density, bright image without contaminating the recording device or causing any trouble. .

Therefore, the recording material of the present invention is excellent not only as a general recording paper but also particularly as a recording material for inkjet recording.

Next, the present invention will be explained in more detail with reference to Examples, Comparative Examples, and Usage Examples. In addition, parts and percentages in the text are based on weight unless otherwise specified.

Example 1 Hardwood bleached kraft pulp (LBKP) and softwood bleached kraft pulp (NBKP) were mixed at a weight ratio of 4=1 to obtain freeness (C, S).

F,) was beaten to 420 ml and used as raw material pulp. For this raw material pulp, 20 parts of talc, 0.0 parts of rosin sizing agent
1 part of aluminum sulfate and 0.02 part of aluminum sulfate to prepare a handmade sheet, and then an aqueous solution containing oxidized starch and salt was applied by air spray at a rate of 0.8 g/m'. A recording material was obtained.

Example 2 30 parts of calcium carbonate, o and oot parts of alkyl ketene dimer, and 0.002 part of cationized starch were blended with the raw material pulp used in Example 1 to prepare a handmade sheet. This surface was coated with polyvinyl alcohol, polyallylamine mM salt (PAA-Hcl-L, manufactured by Nittobo) and polyaminesulfonic acid ammonium salt (RAS-A).
, manufactured by Nittobo) with air spray.
．． The recording material of the present invention was obtained by coating at a rate of 5 g/rn'.

Example 3 LBKP and NBKP were mixed at a weight ratio of 1:4 and beaten to 410 ml of freeness (C, S, F,) to obtain raw material pulp. To this raw material pulp, 35 parts of aluminum silicate, 0.01 part of rosin sizing agent and 0.02j'il of aluminum sulfate! , dispersant (product name Ionet)
MO-400 (manufactured by Sanyo Chemical Industries) and 0.8 parts of calcium chloride were blended to prepare a handmade sheet, and then polyvinylpyrrolidone was applied at a rate of 0.5 g/rrf using a bar coater. Obtained recording materials.

Example 4 To the raw material pulp used in Example 3, 18 parts of calcium carbonate, 0.001 part of alkyl ketene timer, 0.002 part of cationized starch, and a dispersant (trade name: TAM) were added.
DO-10, manufactured by Nikko Chemicals) 0.8 part is blended,
I created a handmade sheet. An aqueous solution containing oxidized starch and Polyfix 601 was applied to this surface using air spray.
．． A recording material of the present invention was obtained by coating at a rate of 8 g/rn'.

Comparative Example 1 Besugrocoat AC (manufactured by Turf Paper Manufacturing Co., Ltd.) was used as a recording material for comparison.

Comparative Example 2 5 parts of talc, 3 parts of silica, 0.01 part of rosin sizing agent, and 0.02 part of aluminum sulfate were added to the raw material valve used in Example 1, and setting was performed to increase thickness variation. Create a handmade sheet in 100 seconds,
A recording material for comparison was obtained.

Comparative Example 3 For the raw material valve used in Example 1, 5 parts of talc, 0.01 part of rosin sizing agent, and 0.02 part of aluminum sulfate were added.
A recording material for comparison was obtained by hand-printing a sheet with a settling time of 100 seconds so as to increase the variation in thickness.

Comparative Example 4 Except that no salt was used in Example 1,
A recording material for comparison was obtained in the same manner as in Example 1.

Comparative Example 5 A comparative recording material was obtained in the same manner as in Example 2, except that polyallylamine hydrochloride and polyamine sulfone quaternary ammonium salt were not used in Example 2.

Comparative Example 6 A comparative recording material was obtained in the same manner as in Example 3 except that calcium chloride was not used in Example 3.

Comparative Example 7 A comparative recording material was obtained in the same manner as in Example 4 except that Polyfix 601 was not used in Example 4.

A recording material for comparison was obtained by removing Polyfix 601 in Example 4.

The pigment coverage of the recording materials of Examples and Comparative Examples obtained above was determined by taking an electron micrograph of the recording surface of the recording material at a magnification of 100 to 300 times, and using a graphic digitizer connected to a computer online. The covered area F was measured, and the entire surface S of the electron micrograph was calculated using the following formula.

Pigment coverage = F/SX100 (%) Usage example The following four types of ink were used to ink the recording materials of Examples 1 to 4 and Comparative Examples 1 to 7 above using a piezo vibrator. On-demand inkjet recording head (discharge orifice diameter 65 m, piezo vibrator drive voltage 6).

Inkjet recording was performed using a recording device having a frequency of 3 V and a frequency of 3.1 KHz.

- Ink (composition) C. 1. Direct Yellow 86 5 parts diethylene glycol 15 parts polyethylene glycol 9200 20 parts water
70 copies RiF'F (composition) C. 1. Acid Red 35 5 parts diethylene glycol 15 parts polyethylene glycol #200 20 parts water
70 Parts of the World (Composition) c. r. Direct Blue 86 5 parts diethylene glycol 15 parts polyethylene glycol #200 20 parts water
70 copies'1! Ink (composition) C. 1. Acid Black 26 5 parts diethylene glycol 15 parts polyethylene glycol #200 20 parts water
70 copies The evaluation results of the recording materials of the Examples and Comparative Examples are shown in Table 1.

Each evaluation item in Table 1 was measured according to the following method.

(1) Ink absorption: 1 second after recording two colors of ink overlappingly, there is no ink flowing out on the surface of the recording material, and if the ink does not flow out even when touched with a finger, O indicates that there is no ink flowing out. However, if the ink flowed out when touched with a finger, it was marked Δ, and otherwise it was marked ×.

(2) Writing panel - 20 people (12 men, 8 women)
A writing test was conducted using five types of pencils: 2H, H, HB, F, and B, and the number of pencils that could be written smoothly was used as a score, and the total score was shown.

(3) Image quality - 20 panelists (12 men, 8 women) answered the question ``Is the image clear?'' for samples with recorded text and graphics, ranging from 5 points to 5 points. 4 good points, 3 points
The total score is shown as 1 point, 2 points as poor, and 1 point as poor.

(4) Dot density JIS K7505 was applied to printed microdots, and black dots were measured using a Sakura microdensidometer PDM-5 (manufactured by Konishiroku Photo Industries).

(5) Measure the area of the dot using a dot shape factor image analysis device, assume a circle with the same area as the dot, calculate its circumference L1, and measure the length L2 of the dot's circumference, Calculated using the following formula.

Dot shape coefficient = LI
Edan A: :
1lln 352 41%
9%U roundabout plan 1 1.3 1.2 1.4
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82nd Ward - Zoichi Naeichi Kai 87 92
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$ 96 $ 94 $ 902 color - 1st base 1.0 1.1 0.9 1.0" 廿紹柁林L ■] - J [] Sho Ichidan Σ Yu 2
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1-115 51 73 89
811 "Rainbow j [Shin 42 Tree 2 58
49 70 plates Saturn parallel recitation 3 90%
78% 70% 671 colors - first base, first and first base 0.8 0.7 0.7 0.9
” Bomono spoon μ Jinichi λJL5L and - Mokudanヱ 11'4 35 $ 41χ 9zU Contour 1.2 1.4 1.1 v-hIJstz 70 $ 45 $1=
'L-upper 0.8 0.9 0.7 Wood 1; Value obtained by dividing the peak height at wavelength 10 cm of the power spectrum of thickness variation by the peak height at wavelength 5 m.

Tree 2: Ink was overflowing in the solid area of the recording material.

Special 1st work applicant: Canon Co., Ltd. Agent: Patent Attorney Yoshi 1) Katsuhiro.

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Claims (4)

[Claims] (1) In a recording material whose main component is fiber, the percentage of the area covered by the pigment on the recording surface of the recording material is 5 to 80%.
The peak height at a wavelength of 10 mm in the power spectrum of the thickness variation of the recording material is 1 of the peak height at a wavelength of 5 mm.
．． 1. A recording material, characterized in that the recording surface is provided with a compound that causes precipitation of the water-soluble dye when an ink containing the water-soluble dye is attached thereto. (2) The recording material according to claim (1), wherein the compound that causes precipitation of a water-soluble dye is a water-soluble metal salt. (3) The recording material according to claim (1), wherein the compound that causes precipitation of the water-soluble dye is an alkali metal and/or alkaline earth metal halide. (4) The compound that causes precipitation of a water-soluble dye is at least one basic oligomer or polymer selected from the following general formulas (I) to (III).
) The recording material described in section 2.). (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R1, R2, and R3 in the above formula are hydrogen atoms, alkyl groups that may have substituents, alkenyl groups, alkanol groups, allyl alkyl groups, allyl alkenyl group, X is an acid group, m is an integer from 1 to 7, and n is an integer from 2 to 10.) (II) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (R1, R2, R3 in the above formula (III ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R1 and R2 in the above formula are hydrogen atoms, alkyl groups that may have substituents, alkenyl groups, alkanol groups, allyl alkyl groups, allyl alkenyl groups, represents an acid group, and n represents an integer from 5 to 100,000.)