KR20060094903A - Paper feed roll manufacturing composition, paper feed roll and manufacturing method thereof - Google Patents

Abstract

Providing the thermosetting urethane elastomer composition which can manufacture the paper feed roll which is excellent in the liquid stability of a hardening | curing agent, and is excellent in mechanical property and surface property.

The subject matter [A] containing the NCO group terminal urethane prepolymer obtained by reaction of MDI isocyanate and PTMG, whose NCO content is 5 to 15%, and the viscosity in 75 degreeC is 1,000 mm <2> / s or less; (B1) long-chain diols made of PTMG, (B2) short-chain diols containing 2-methyl-1,3-propanediol in a proportion exceeding 50% by mass, (B3) short-chain triols having TMP as an essential component, ( B4) hardening agent [B] containing the catalyst which becomes DMI, and the thermosensitive catalyst which becomes (B5) bicyclic tertiary diamine (salt); The ratio [(B1) / [(B2) + (B3)]] is 80/20 to 95/5 (mass), and the ratio [(B2) + (B3)] is 55/45 to 95/5 (mass) to be.

Paper feed rolls, urethane elastomer compositions, long chain diols, short chain diols, thermosensitive catalysts

Description

Composition for paper feed roll manufacturing, paper feed roll and manufacturing method thereof

Technical Field

The present invention relates to a composition for producing a paper feed roll, a paper feed roll, and a method for producing the same, and more particularly, to a thermosetting urethane elastomer composition for forming an elastic member of a paper feed roll, and the composition. It relates to a paper feed roll and a manufacturing method thereof.

Background

Urethane elastomer is used as an elastic member (coating layer of a core) of a paper feed roll (refer patent document 1-3 below).

In the manufacturing method of the elastic member (urethane elastomer) of a paper feed roll, the prepolymer method is employ | adopted from a viewpoint of avoiding deterioration of the working environment by a premonomer. In this prepolymer method, isocyanate is reacted with a long-chain polyol such as poly (oxytetramethylene) glycol (PTMG) to prepare a main body of the NCO group-terminated urethane prepolymer, A curing agent containing short-chain diol (1,4-BD), short-chain triol (TMP) and a catalyst (TEDA, etc.) is prepared. And an elastic member is formed by mixing a main body and a hardening | curing agent and hardening | curing in a shaping | molding die.

By the way, in the prepolymer method, since the viscosity of a subject becomes excessive, handling property is inferior. Moreover, since the difference of the mixing ratio of a main material and a hardening | curing agent is large (for example, 100/3-100/10), there exists a problem that uniform mixing operation becomes difficult.

Therefore, the semi-prepolymer method which uses a part of long chain polyol (PTMG) for synthesis | combination of a prepolymer, and uses the remainder of long chain polyol (PTMG) as a component of a hardening | curing agent is employ | adopted.

Further, as a molding polyurethane-based elastomer composition (composition by the semi-prepolymer method) for forming a molded article such as a paper feed roll, it contains an NCO-group-terminated urethane prepolymer obtained by the reaction of MDI isocyanate and PTMG. A liquid (the subject) to be prepared, and 1,4-BD, the B liquid (curing agent) containing glycol having an alkyl side chain in the main chain having 3 to 8 carbon atoms, PTMG and a catalyst, 1 The composition whose ratio of the glycol which has an alkyl side chain with respect to, 4-BD is 5-100 mol% is disclosed (refer patent document 4).

According to this composition, as short chain diol which comprises a hardening | curing agent, since the glycol which has an alkyl side chain with 1, 4-BD is contained in a fixed ratio, the transparent molded article which has high hardness can be formed.

However, in the semi-prepolymer method, since compatibility is limited between 1,4-BD (short chain diol) and PTMG (long chain diol) which are components of a hardening | curing agent, it is difficult to mix them homogeneously. Do. For this reason, when the prepared hardening | curing agent is cooled to room temperature and it solidifies, when this is reheated and melt | dissolved, the problem that both will separate into two layers arises.

Moreover, also in the composition disclosed by following patent document 4, since the compatibility of the components of a hardening | curing agent is low and the liquid stability of a hardening | curing agent is low, the problem of phase separation after melting by reheating cannot be solved.

On the other hand, in the case of using TEDA as a catalyst, if a certain amount is added to secure the necessary curing property (hardening speed) from the viewpoint of productivity, etc., the molding time (pot life) becomes short and operation is impossible. In some cases, the operability may be very poor. In addition, if the amount of use is kept low enough to secure the required mold time, the curability may be insufficient, requiring considerable time until demolding, or sticking to the surface of the molded article after demolding.

Such a problem becomes remarkable as the ratio of the glycol having an alkyl side chain to the short chain diol constituting the curing agent becomes higher (by this, the crystallinity of the resulting cured product is lowered). In addition, stickiness of the surface of a molded article becomes a remarkable problem when obtaining the hardened | cured material of comparatively low hardness (for example, 40-70 by JIS-A hardness).

Sticky molded articles (rolls) cause problems such as mutual adhesion when they are stacked and stored.

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-35937

[Patent Document 2] Japanese Patent Application Laid-Open No. 2002-68515

[Patent Document 3] Japanese Patent Application Laid-Open No. 2004-51249

[Patent Document 4] Japanese Patent Application Laid-Open No. 8-283368

A first object of the present invention is to provide a composition for producing a paper feed roll (a thermosetting urethane elastomer composition) by a semi-prepolymer method having high compatibility of components (long-chain diol and short-chain polyol) of the curing agent and excellent liquid stability of the curing agent. It is in doing it.

The second object of the present invention is to provide a mold having a low mold viscosity, which can sufficiently secure necessary mold time, excellent operability, a high curing speed, and a roll having a non-sticky surface even after demolding in a short time. It is an object of the present invention to provide a composition for producing a paper feed roll, which is also excellent in productivity (roll productivity).

A third object of the present invention is to provide a composition for producing a paper feed roll which can form a cured product having the mechanical properties required for the elastic member of the paper feed roll.

A fourth object of the present invention is to provide a composition for producing a paper feed roll, which can form a cured product having a surface property (high friction coefficient and stability thereof suitable as an elastic member of the paper feed roll.

A fifth object of the present invention is to provide a paper feed roll excellent in productivity, mechanical properties of an elastic member, surface properties, and stability thereof, and a manufacturing method thereof.

The composition for manufacturing a paper feed roll of the present invention is a thermosetting urethane elastomer composition used to form an elastic member of a paper feed roll, and is an NCO group obtained by the reaction of an MDI isocyanate and poly (oxytetramethylene) glycol (PTMG). The main [A] having an NCO content of 5 to 15% and a viscosity at 75 ° C of 1,000 mm 2 / s or less, containing a terminal urethane prepolymer;

(B1) long chain diols as PTMG,

(B2) short-chain diols containing 2-methyl-1,3-propanediol in proportions exceeding 50 mass%,

(B3) short-chain triol containing trimethylolpropane (TMP) as an essential component,

(B4) a catalyst consisting of 1,2-dimethylimidazole (DMI),

(B5) 1,5-diazabicyclo [4. 3. 0] nonene-5 (DBN), salt of DBN, 1,8-diazabicyclo [5. 4. A curing agent containing a thermosensitive catalyst composed of at least one bicyclic tertiary diamine (salt) selected from undecene-7 (DBU) and a salt of DBU [B] ];

The ratio [(B1) / [(B2) + (B3)]] of the content of the long chain diol (B1) and the total content of the short chain diol (B2) and the short chain triol (B3) is 80/20 to 95/5 (Mass),

The ratio [(B2) / (B3)] between the content of the short chain diol (B2) and the content of the short chain triol (B3) is 55/45 to 95/5 (mass).

In the composition of the present invention, the catalyst (B4) and the catalyst (B5) are 0.01 to 100 parts by mass based on 100 parts by mass of the polyol component including the long chain diol (B1), the short chain diol (B2), and the short chain triol (B3). It is contained in the ratio of 5 mass parts, and it is preferable that the content rate [(B4) / (B5)] with a catalyst (B4) and a catalyst (B5) is 100/5-100/50 (mass).

Moreover, it is preferable to contain a plasticizer [C].

The paper feed roll of the present invention is characterized by comprising an elastic member having a JIS-A hardness of greater than 60 and 70 or less formed by curing the composition of the present invention containing no plasticizer in a mold.

Moreover, the paper feed roll of this invention is provided with the elastic member whose JIS-A hardness is 40-60 formed by hardening the composition of this invention containing a plasticizer in a shaping | molding die.

The manufacturing method of this invention includes the process of hardening | curing the composition of this invention which does not contain a plasticizer in a shaping | molding die, and forming the elastic member whose JIS-A hardness exceeds 60 and is 70 or less.

Moreover, the manufacturing method of this invention includes the process of hardening | curing the composition of this invention containing a plasticizer in a shaping | molding die, and forming the elastic member whose JIS-A hardness is 40-60.

(1) The composition of the present invention has high compatibility with long-chain diols (B1), which are components of the curing agent, and short-chain polyols (short-chain diols (B2) and short-chain triols (B3)), and is excellent in liquid stability of the curing agent. . Therefore, when the curing agent solidified at room temperature is reheated and melted, its components do not phase separate.

(2) The composition of the present invention has a low mold viscosity, can sufficiently secure the required mold time, is excellent in operability, has a high curing rate, and can obtain a roll having a non-sticky surface even after demolding in a short time. (Roll productivity) is also excellent.

(3) According to the composition of this invention, the hardened | cured material with the mechanical characteristic calculated | required by the elastic member of a paper feed roll can be formed.

(4) According to the composition of this invention, the hardened | cured material provided with the surface characteristic (high friction coefficient) suitable for the elastic member of a paper feed roll, and its stability can be formed.

(5) The paper feed roll of the present invention has excellent productivity and is not sticky to the surface of the elastic member constituting the same, and furthermore, excellent mechanical properties, surface properties and stability thereof.

Best Mode for Solving the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The composition of the present invention is a thermosetting urethane elastomer composition for use in forming an elastic member of a paper feed roll, comprising: a mains [A] containing an NCO group-terminated urethane prepolymer; Curing agent [B] containing long-chain diol (B1), short-chain diol (B2), short-chain triol (B3), catalyst (B4) to be DMI, and thermosensitive catalyst (B5) to be bicyclic tertiary diamine (salt) It becomes

<Topic [A]>

The NCO group terminal urethane prepolymer which is an essential component of the main ingredient [A] is obtained by reaction of MDI type isocyanate and PTMG.

As NCO content of the main ingredient [A] containing such an NCO group terminal urethane prepolymer, it is 5-15 mass% normally.

Moreover, as viscosity (75 degreeC) of the main body [A] containing an NCO group terminal urethane prepolymer, it is 1,000 mm <2> / s or less normally, Preferably it is 500 mm <2> / s or less.

As MDI type isocyanate provided in preparation of NCO group terminal urethane prepolymer, 4,4'- diphenylmethane diisocyanate (4,4'-MDI) and 2,4'- diphenylmethane diisocyanate (2,4'- MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI); Liquid MDIs, such as these carbodiimide modified bodies (carbodiimide modified MDI) and uretonimine modified bodies (uretonimide-ized MDI), can be illustrated, These can be used individually or in combination of 2 or more types.

As average molecular weight of PTMG provided for preparation of an NCO group terminal urethane prepolymer, it is preferable that it is 500-5,000, More preferably, it becomes 800-3,000.

The main ingredient [A] can be prepared by reacting MDI isocyanate and PTMG at a ratio such that the NCO group of the former is more than the OH group of the latter.

It is preferable that NCO / OH (molar ratio) is 1.5-30.0 here, More preferably, it is 2.0-10.0.

This reaction is preferably carried out in a reaction vessel substituted with nitrogen.

It is preferable that reaction temperature is 60-100 degreeC, More preferably, it is 70-90 degreeC.

Moreover, in this reaction, you may use well-known urethanization catalysts, such as an organometallic type and an amine type, as needed.

Moreover, you may use a chain extender together in this reaction system as needed. That is, the prepolymer obtained by making MDI type isocyanate, PTMG, and a chain extender react is also contained in the "NCO group terminal urethane prepolymer" which comprises main body [A].

As such a chain extender, the compound similar to what is used as short-chain diol (B2) mentioned later is mentioned.

The main body [A] obtained in this manner is filled in an accommodating container at the reaction temperature, and the air gap of the vessel is nitrogen-substituted and then tightly cooled.

<Hardening agent [B]>

The long-chain diol (B1) constituting the curing agent [B] is PTMG, and the average molecular weight thereof is preferably 500 to 5,000, more preferably 700 to 3,000.

Short-chain diol (B2) which comprises hardening | curing agent [B] is short-chain diol which contains 2-methyl- 1, 3- propanediol in the ratio exceeding 50 mass%.

As molecular weight of the diol which comprises short-chain diol (B2), it is preferable that it is 50-300, More preferably, it is 60-250.

Examples of short-chain diols other than 2-methyl-1,3-propanediol which can be used as the short-chain diol (B2) include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1 Short-chain diol which does not have side chains, such as a 20-eico-acid diol, is mentioned, Among these, 1, 4- butanediol is preferable.

As the ratio of 2-methyl-1,3-propanediol to the short-chain diol (B2), it is usually a ratio exceeding 50 mass%, preferably 55 mass% or more, more preferably 60 mass% or more, Especially preferably, it becomes 65 mass% or more.

Short-chain diols having a proportion of 2-methyl-1,3-propanediol of 50% by mass or less have low compatibility with PTMG (long-chain diols), and thus, the resulting hardener cannot solve the problem of phase separation after melting by reheating. (See Comparative Example 1 described later.)

Suitable short-chain diols (B2) include a mixture of 55-100 mass% of 2-methyl-1,3-propanediol and 45-0 mass% of 1,4-butanediol.

Short-chain triol (B3) which comprises hardening | curing agent [B] has TMP as an essential component.

As molecular weight of the triol which comprises short-chain triol (B3), it is preferable that it is 50-400, More preferably, it is 70-300.

Examples of short-chain triols other than TMP that can be used as short-chain triols (B3) include glycerin and hexanetriol (including various isomers).

As a ratio of TMP which occupies for short-chain triol (B3), it is preferable that it is 50 mass% or more, More preferably, it is 60 mass% or more, Especially preferably, it is 100 mass%.

By containing short-chain triol (B3), a crosslinked structure is introduce | transduced into the hardened | cured material obtained, and this hardened | cured material becomes what has the mechanical characteristic calculated | required by the elastic member of a paper feed roll.

As a ratio [(B1) / [(B2) + (B3)]] with content of long-chain diol (B1) and total content of short-chain diol (B2) and short-chain triol (B3), it is 80/20-95 normally It is / 5 (mass), Preferably it is 85/15-90/10 (mass).

When this ratio is less than 80/20 (long chain diol is too low), the compatibility of a component becomes very low and a homogeneous hardening agent cannot be prepared (refer comparative example 3 mentioned later).

On the other hand, when this ratio exceeds 95/5 (excessive long-chain diol), the compression set of the cured product formed by the composition containing the resulting curing agent is excessive, resulting in excessive paper transport. It does not have the compression characteristic required for the elastic member of a roll. Moreover, the hardened | cured material is easy to change its surface characteristic (friction coefficient), and its durability as a paper feed roll is inferior (refer comparative example 4 mentioned later).

As a ratio [(B2) / (B3)] of content of short-chain diol (B2) and content of short-chain triol (B3), it becomes 55/45-95/5 (mass) normally, Preferably it is 55/45 90/10 (mass), More preferably, it is 60/40-90/10 (mass), Especially preferably, it becomes 70/30-90/10 (mass).

When this ratio is less than 55/45 (short-chain diol is too low), the tensile strength and tear strength of the cured product formed from the composition containing the resulting curing agent are too low. It does not have the mechanical properties required for the elastic member. Moreover, although the said hardened | cured material is excellent in compression characteristic, the surface characteristic (friction coefficient) tends to change, and durability as a paper feed roll is inferior. In addition, cracks may be generated during use due to low tensile strength and tear strength (see Comparative Example 5 described later).

On the other hand, when this ratio exceeds 95/5 (excessive short-chain diol), when the hardening | curing agent obtained is cooled to room temperature and it solidifies, it reheats and fuses, and a component will separate into two layers ( See Comparative Example 2 described later).

In the composition of the present invention, as a catalyst constituting the curing agent [B], a catalyst (B4) made of DMI (1,2-dimethylimidazole) and a thermosensitive catalyst made of a bicyclic tertiary diamine (salt) ( B5) is used in combination.

In order to solve the problem of phase separation at the time of melting of a hardening | curing agent, when using short-chain diol (B2) which contains 2-methyl- 1, 3- propanediol in the ratio exceeding 50 mass% as a component of a hardening | curing agent. In the case of using TEDA, which is widely used as a catalyst, curing of the resulting composition (a mixture of a main agent and a curing agent) is insufficient, requiring considerable time until demolding, or sticking to the surface of the cured product (molded product) after demolding. (See Comparative Example 8 described later.)

And such a problem can be solved by using the thermosensitive catalyst (B5) which becomes bicyclic tertiary diamine (salt) as a catalyst which replaces TEDA.

However, when a composition (a mixture of a main agent and a curing agent) containing only a bicyclic tertiary diamine (salt) reaches a certain temperature, the curing reaction proceeds rapidly, but allophanate is formed together with the urethanization reaction. Side reactions, such as biuretization and isocyanuration, tend to occur, resulting in insufficient polymerization, and thus the cured product obtained in this manner has a large compressive permanent distortion (see Comparative Example 7 described later).

Therefore, by using the thermosensitive catalyst (B5) in combination with a catalyst (B4) of relatively reactive DMI that promotes urethanization, the rapid reactivity of the composition is reduced, no stickiness is applied to the surface, and the polymer is sufficiently polymerized. It is possible to form the cured product (elastic member of the paper feed roll).

The thermosensitive catalyst (B5) has a low initial reactivity, and is a catalyst capable of rapidly advancing the reaction when reaching a constant temperature (for example, 60 to 110 ° C).

The thermosensitive catalyst (B5) is composed of DBN (1,5-diazabicyclo [4.3.0] nonene-5), salt of DBN, DBU (1,8-diazabicyclo [5.4.0] undecene- 7) and at least one bicyclic tertiary diamine (salt) selected from salts of DBU.

As a salt of DBN and a salt of DBU, these formate, octylate, etc. can be illustrated.

As the usage-amount (total amount of quantum) of catalyst (B4) and catalyst (B5), it is 0.01-5 mass parts with respect to 100 mass parts of polyol components which become long chain diol (B1), short chain diol (B2), and short chain triol (B3). It is preferable.

It is preferable that the usage-amount (total amount of both catalysts) in the composition which does not contain a plasticizer is 0.01-1 mass part with respect to 100 mass parts of polyol components, More preferably, it is 0.03-0.8 mass part, Especially preferably, Becomes 0.05-0.5 mass part.

It is preferable that the usage-amount of the catalyst in the composition containing a plasticizer is 0.01-5 mass parts with respect to 100 mass parts of polyol components, More preferably, it is 0.03-3 mass parts, Especially preferably, it is 0.05-1 mass part. .

When the amount of use of the catalyst (B4) and the catalyst (B5) is too small, the curing reaction of the resulting composition requires a long time, or the cured product formed from the composition is required for the elastic member of the paper feed roll. It does not have mechanical properties.

On the other hand, when the usage-amount (the total amount of quantum) of an catalyst is excessive, the pot life of the composition obtained becomes extremely short, and mold operation becomes impossible or difficult. Moreover, the bleed of a catalyst may generate | occur | produce on the surface of the hardened | cured material formed by this composition, and a paper may be contaminated.

As content ratio [(B4) / (B5)] of catalyst (B4) and catalyst (B5), it is preferable that it is 100/5-100/50 (mass), More preferably, it is 100/8-100/40, Especially preferably, it becomes 100/10-100/30.

When the ratio of the catalyst (B4) is excessive (the ratio of the catalyst (B5) is too low), it is not possible to balance the securing of the required molding time and the high curing rate in the composition obtained.

On the other hand, when the ratio of the catalyst (B4) is under [the ratio of the catalyst (B5) is excessive], the hardened | cured material formed from the composition obtained may yellow or become brittle.

Curing agent [B] can be prepared by mixing a long chain diol (B1), a short chain diol (B2), a short chain triol (B3), a catalyst (B4), a catalyst (B5), and arbitrary components mentioned later, heating.

Here, it is preferable that the temperature at the time of mixing is 40-80 degreeC, More preferably, it is 50-70 degreeC.

The curing agent [B] thus obtained is filled into the storage container at the temperature at the time of mixing, and after tightly nitrogen-substituting the voids of the container, it is tightly cooled. As a result, the curing agent [B] is solidified.

<Plasticizer [C]>

It is preferable that the plasticizer [C] is further contained in the composition of this invention.

By use of a plasticizer [C], the viscosity of the composition obtained can be adjusted, and the mechanical characteristic (hardness) and surface characteristic (friction coefficient) of the hardened | cured material formed from this composition can be adjusted.

Specifically, according to the specification, the hardness of the cured product is adjusted to 40 to 60, the friction coefficient on the surface of the cured product is set to be constant or higher, and the paper sheet separation function can be reliably expressed in the roll obtained.

Examples of such a plasticizer [C] include adipate-based plasticizers such as dibutyl glycol adipate and dibutyl carbitol adipate; Phosphate plasticizers such as cresyl diphenyl phosphate, tributyl phosphate, trioctyl phosphate and tributoxyethyl phosphate; commercially available as "RS700" (manufactured by Asahi Denka Co., Ltd.) and "RS735" (manufactured by the same company). Polyether ester plasticizer; Polyether plasticizer marketed as "RS705" (the company make); Phthalate plasticizers, such as DOP and DINP; Aromatic hydrocarbon-type plasticizer marketed as "Niseki Hysol SAS-269" (made by Shin-Nippon Sekiyu Co., Ltd.), "Niseki Hysol SAS-LH" (the company make) Etc. can be mentioned.

Although the plasticizer [C] can be used by mix | blending in advance as at least one structural component of the main body [A] and the hardening agent [B], it is preferable to mix | blend in a main body [A]. Thereby, the viscosity of the main body [A] falls, and the casting operation of the composition of this invention obtained by mixing and mixing this and hardening | curing agent [B] can be performed easily.

As the usage-amount of plasticizer [C], it is 5-with respect to 100 mass parts of resin components which become NCO group terminal urethane prepolymer, long chain diol (B1), short chain diol (B2), and short chain triol (B3) which comprise main body [A]. It is preferable that it is 80 mass parts, More preferably, it is 10-40 mass parts.

When the usage-amount of plasticizer [C] is too small, the effect by mix | blending a plasticizer (for example, the effect of preventing the fall of the friction coefficient of the hardened | cured material surface) cannot fully be exhibited. On the other hand, when the usage-amount of plasticizer [C] is excessive, the mechanical properties (hardness and intensity | strength) of hardened | cured material will fall significantly, and the intrinsic wear resistance of a urethane elastomer is impaired. Moreover, roll workability (especially abrasiveness) tends to worsen.

<Other optional ingredients>

The composition of this invention may contain various arbitrary components as needed.

Examples of such optional components include dyes, pigments, fillers, conductive agents, antioxidants, ultraviolet absorbers, hydrolysis inhibitors, antibacterial agents, and the like.

The composition of the present invention is a composition for use in order to form an elastic member of a paper feed roll, but the same composition as this is used for applications other than the elastic member of the paper feed roll (in particular, a high coefficient of friction and stability thereof are required. It can also be applied to).

<Production method of the present invention>

The manufacturing method of this invention is a manufacturing method of the paper feed roll containing the process of hardening | curing the composition of this invention in a shaping | molding die, and forming an elastic member.

When an example of the manufacturing method of this invention is shown, each of the main body [A] and the hardening | curing agent [B] is heated (reheated) at 60 degreeC, they are mixed at the same temperature, pressure reduction defoaming treatment, It is made into a composition, it is inject | poured into the shaping | molding die in which the roll core is arrange | positioned, and it hardens by heat.

Thereby, the paper feed roll by which the surface of the roll core was coat | covered with the hardened | cured material (elastic member) can be obtained.

Here, as a mixing ratio of the main body [A] and the hardening agent [B], it is preferable that it is a ratio which becomes molar ratio (NCO / OH) of NCO group which an former has, and OH group which the latter has which is 0.8 / 1-1.2 / 1. More preferably, it becomes the ratio which becomes 0.9 / 1-1.1 / 1.

Moreover, it is preferable that the mold release agent is apply | coated to the surface of a shaping | molding die. Examples of such a release agent may be mentioned a fluorine-based, silicone-based, wax-based releasing agent such as generally used.

According to the manufacturing method of this invention, a hardening reaction can be completed in a short time, and even if it demolds in a short time, the roll which has a non-sticky surface resulting from an unreacted NCO group or OH group can be obtained.

<Paper feed roll of the present invention>

The paper feed roll of this invention is a paper feed roll shown to following (1) or (2).

(1) A paper feed roll comprising an elastic member having a JIS-A hardness of greater than 60 and 70 or less formed by curing the composition of the present invention that does not contain a plasticizer in a molding die (hereinafter, referred to as "first Paper feed roll).

(2) A paper feed roll comprising an elastic member having a JIS-A hardness of 40 to 60, which is formed by curing the composition of the present invention containing a plasticizer in a molding die (hereinafter referred to as "second paper feed roll Also called.

The elastic member constituting the paper feed roll of the present invention has excellent mechanical properties, suitable surface properties (high coefficient of friction and stability thereof), and good appearance.

JIS-A hardness of the elastic member which comprises a 1st paper feed roll exceeds 60 and becomes 70 or less. While this elastic member has the property of complete amorphous (non-crystalline), it does not generate | occur | produce a sticky point etc. in the surface.

The first paper feed roll can be suitably used as a sheet conveying roll mounted on a copying machine, a printer, or the like, or a bill conveying roll mounted on an ATM, a vending machine, or the like.

JIS-A hardness of the elastic member which comprises a 2nd paper feed roll is 40-60. And although it is such a comparatively low hardness, stickiness etc. do not generate | occur | produce on the surface of the said elastic member.

The second paper feed roll is required to have a sheet separation function such as a pick-up roll, a feed roll, a retard roll, and the like, which is mounted in a feeder such as a copier or a printer. It can be used suitably as a paper feed roll.

Example

<Preparation Example 1>

According to the prescription shown in Table 1 below, MDI isocyanate and PTMG were added to a reaction vessel substituted with nitrogen, and reacted at 80 ° C for 4 hours to obtain an NCO-group-terminated urethane prepolymer (the completion of the reaction was performed by titration of NCO content). Then, this was filled into an accommodating container, and the space | gap of this container was nitrogen-substituted, and it sealed and cooled to room temperature, and obtained the subject [A] [topic (A-1)].

The NCO content and viscosity (75 ° C.) of the subject (A-1) of the NCO group terminated urethane prepolymer are shown together in Table 1 below.

<Preparation Example 2-5>

According to the formulation shown in Table 1 below, MDI isocyanate and PTMG were placed in a nitrogen-substituted reaction vessel and reacted at 80 ° C for 4 hours to obtain an NCO-group-terminated urethane prepolymer (the completion of the reaction was confirmed by titration of NCO content), After adding a plasticizer to this and stirring-mixing it for about 1 hour, it filled it into a receiving container, and made it airtight after nitrogen-substituting the space | gap of the said container, and was carried out. ] Were obtained.

About each of the main (A-2)-(A-5) which becomes an NCO group terminal urethane prepolymer and a plasticizer, NCO content and a viscosity (75 degreeC) are shown together in Table 1 below.

* 1) MDI: The ratio occupied by "Millionate (registered trademark) MT" (made by Nippon Polyurethane Co., Ltd.) and 4,4'-MDI is 99 mass% or more.

* 2) Carbodiimide modified liquid MDI: "Millionate (trademark) MTL" (made by Nippon Polyurethane Co., Ltd.).

* 3) "PTG-850SN": PTMG (manufactured by Hodogaya Kagaku Kogyo Co., Ltd.) with an average molecular weight of 850.

* 4) "PTG-1000SN": PTMG (manufactured by Hodogaya Kagaku Kogyo Co., Ltd.) with an average molecular weight of 1,000.

* 5) "PTG-2000SN": PTMG (manufactured by Hodogaya Kagaku Kogyo Co., Ltd.) with an average molecular weight of 2,000.

* 6) Hydrocarbon plasticizer: "Niseki Hysol (registered trademark) SAS-LH" (made by Shin-Nippon Sekiyu Kagaku Co., Ltd.)

<Example 1>

Curing agent by mixing long chain diol (B1), short chain diol (B2), short chain triol (B3), catalyst (B4), and thermosensitive catalyst (B5) under 60 ° C. heating for 1 hour according to the formulation formulation shown in Table 2 below. [B] was prepared. The state of the hardening | curing agent [B] immediately after preparation (liquid temperature = 60 degreeC) was visually observed, and the homogeneous state was shown without being suspended or phase-separating. The obtained hardening | curing agent [B] was filled in the accommodating container, and the space | gap of this container was nitrogen-substituted, and it sealed tightly and cooled to room temperature. Thereby, hardening | curing agent [B] solidified.

Subsequently, the curing agent [B] was heated (reheated) at 60 ° C. and the state of the curing agent [B] melted thereby was visually observed. As a result, a homogeneous state was shown without phase separation.

Subsequently, the composition of the present invention is prepared by mixing the main body (A-1) heated to 60 ° C and the curing agent [B] (liquid temperature = 60 ° C), and the following items (1) to (8) ) Was measured or evaluated. The results are shown in Table 4 below.

(1) mold viscosity:

After mixing main material (A-1) and hardening | curing agent [B], the viscosity in 2 minutes after was made into the "mould viscosity", and this was measured. From the viewpoint of mold operability, the mold viscosity needs to be 4,000 mPa · s or less, and preferably 2,000 mPa · s or less.

(2) Port Life:

After mixing the main body [A] and the hardening agent [B], the time until the viscosity of the mixture (composition of the present invention) reached 100,000 mPa · s (130 ° C.) was measured as “port life”. From the standpoint of mold operability, the pot life is preferably about 5 to 15 minutes.

(3) demoulding time:

The composition of this invention was inject | poured in the shaping | molding die, and the demoldable time when heat-hardened at 130 degreeC was measured. Here, "deformation possible time" means the time which can demold easily without breaking and a crack, and maintaining a roll shape, and needs to be within 60 minutes from a viewpoint of moldability (productivity), It is preferable to be within 30 minutes.

(4) the stickiness of the surface:

After inject | pouring the composition of this invention into a shaping | molding die, and hardening | curing at 130 degreeC for 60 minutes of heating conditions, the obtained hardened | cured material was left still for 7 days at room temperature, and the surface was touched with a finger and the presence or absence of stickiness was confirmed. It was.

(5) Mechanical properties of the cured product:

After inject | pouring the composition of this invention into a shaping | molding die and hardening | curing at 130 degreeC for 60 minutes of heating conditions, after leaving the hardened | cured material obtained for 7 days at room temperature, a test piece is produced from this hardened | cured material, and JISK In accordance with 7321, mechanical properties [JIS-A hardness, tensile strength, elongation, tear strength, compressive permanent distortion (25% compression, 70 ° C. × 22 hours)] were measured.

(6) Surface characteristics (friction coefficient) of hardened | cured material:

The composition of this invention was inject | poured in the shaping | molding die in which the roll core is arrange | positioned, and it hardened | cured at 130 degreeC for 60 minutes of heating conditions, and produced the paper feed roll by which the surface of the roll core was coat | covered with hardened | cured material (elastic member). .

The coefficient of friction (mu) at the surface (surface of the hardened product) of the paper feed roll thus obtained was measured. The coefficient of friction of the surface required for the paper feed roll needs to be 1.4 or more.

(7) stability of surface properties (durability as roll):

After mounting the paper feed roll obtained by said (6) to a machine (copier), and performing 100,000 times paper conveyance, it carried out similarly to said (6), and carried out in the surface of the paper feed roll The coefficient of friction (μ) was measured and its change rate [(μo-μ) / μo] was obtained. This rate of change needs to be 20% or less.

(8) presence or absence of crack generation (durability as a roll):

After the paper feed roll obtained by the above (6) was mounted on a machine (copier) to make 100,000 paper feeds, the surface of the roll was observed to investigate the occurrence of cracks.

<Examples 2 to 21>

In accordance with the formulations shown in Tables 2 and 3 below, a curing agent [B] was prepared in the same manner as in Example 1 except that the component ratios of the constituents were changed. As a result of visual observation of the state immediately after preparation (liquid temperature = 60 degreeC) about each obtained hardening | curing agent [B], neither hardening agent [B] was suspended or showed a homogeneous state without phase separation. Each of the obtained curing agents [B] was filled in an accommodating container, and the pores of the vessel were nitrogen-substituted and then tightly cooled to room temperature (by which, each of the curing agents [B] was solidified).

Then, each of the curing agents [B] was heated (reheated) at 60 ° C., and the state of the melted curing agent [B] was visually observed. As a result, no curing agent [B] was homogeneous without phase separation. Was showing.

Next, the composition of the present invention is prepared by mixing the main ingredient [A] (liquid temperature = 60 ° C) and the curing agent [B] (liquid temperature = 60 ° C) shown in Tables 2 and 3 below. The measurement or evaluation of the items (1) to (8) was performed. The results are shown in Tables 4 and 5 below.

* 5) "PTG-2000SN": PTMG (manufactured by Hodogaya Kagaku Kogyo Co., Ltd.) with an average molecular weight of 2,000.

* 7) "2ME1, 3PD": 2-methyl-1,3-propanediol

Comparative Example 1

In accordance with the formulation formulation shown in Table 6 below, a curing agent was prepared by mixing the components (long chain diol, short chain diol, short chain triol) under heating at 60 ° C for 1 hour. The state of the hardening | curing agent immediately after preparation (liquid temperature = 60 degreeC) was observed visually, and it showed the homogeneous state, without phase-separation. The obtained hardening | curing agent was filled into the accommodating container, and the space | gap of this container was nitrogen-substituted, and was made tight, and it cooled to room temperature. This hardened | cured the agent.

Then, the curing agent was warmed (reheated) to 60 ° C., and the state of the melted agent was visually observed, whereby phase separation of the components was recognized. For this reason, the mixing operation with the subject was not performed.

This comparative example 1 is a comparative example of 50 mass% (50 mass% or less) of the ratio of 2-methyl- 1, 3- propanediol which occupies for short-chain diol.

Comparative Example 2

In accordance with the formulation formulation shown in Table 6 below, a curing agent was prepared by mixing the components (long chain diol, short chain diol, short chain triol) under heating at 60 ° C for 1 hour. The state of the hardening | curing agent immediately after preparation (liquid temperature = 60 degreeC) was observed visually, and it showed the homogeneous state, without phase-separation. The obtained hardening | curing agent was filled into the accommodating container, and the space | gap of this container was nitrogen-substituted, and was made tight, and it cooled to room temperature. This hardened | cured the agent.

Then, the curing agent was warmed (reheated) to 60 ° C., and the state of the melted agent was visually observed, whereby phase separation of the components was recognized. For this reason, the mixing operation with the subject was not performed.

This comparative example 2 is a comparative example in which the mass ratio between the content of the short chain diol and the content of the short chain triol is 96/4 (> 95/5).

Comparative Example 3

In accordance with the formulation formulation shown in Table 6 below, a curing agent was prepared by mixing the components (long chain diol, short chain diol, short chain triol) under heating at 60 ° C for 1 hour. As a result of observing the state of the hardening | curing agent immediately after preparation (liquid temperature = 60 degreeC) visually, as a suspended state, phase separation occurred shortly after. The obtained hardening | curing agent was filled into the accommodating container, and the space | gap of this container was nitrogen-substituted, and was made tight, and it cooled to room temperature. This hardened | cured the agent.

Then, the curing agent was warmed (reheated) to 60 ° C., and the state of the melted agent was visually observed, whereby phase separation of the components was recognized. For this reason, the mixing operation with the subject was not performed.

This comparative example 3 is a comparative example in which the ratio between the content of the long chain diol (B1) and the total content of the short chain diol (B2) and the short chain triol (B3) is 78/22 (<80/20).

<Comparative Example 4>

In accordance with the formulation formulation shown in Table 6 below, a curing agent was prepared by mixing the components (long chain diol, short chain diol, short chain triol, catalyst) under heating at 60 ° C for 1 hour. The state of the hardening | curing agent immediately after preparation (liquid temperature = 60 degreeC) was observed visually, and it showed the homogeneous state, without phase-separation. The obtained hardening | curing agent was filled into the accommodating container, and the space | gap of this container was nitrogen-substituted, and was made tight, and it cooled to room temperature. This hardened | cured the agent.

Then, the curing agent was heated (reheated) at 60 ° C, and the state of the curing agent melted by the naked eye was observed, and as a result, it showed a homogeneous state without phase separation.

Subsequently, the composition for comparative was prepared by mixing the main body (A-5) heated at 60 degreeC, and this hardening | curing agent (liquid temperature = 60 degreeC), The measurement of said item (1)-(8) about the composition obtained To evaluation. The results are shown in Table 7 below.

This comparative example 4 is a comparative example in which the ratio of the content of the long chain diol (B1) to the total content of the short chain diol (B2) and the short chain triol (B3) is 96/4 (> 95/5).

Comparative Example 5

In accordance with the formulation formulation shown in Table 6 below, a curing agent was prepared by mixing the components (long chain diol, short chain diol, short chain triol, catalyst) under heating at 60 ° C for 1 hour. The state of the hardening | curing agent immediately after preparation (liquid temperature = 60 degreeC) was observed visually, and it showed the homogeneous state, without phase-separation. The obtained hardening | curing agent was filled into the accommodating container, and the space | gap of this container was nitrogen-substituted, and was made tight, and it cooled to room temperature. This hardened | cured the agent.

Then, the curing agent was heated (reheated) at 60 ° C, and the state of the curing agent melted by the naked eye was observed, and as a result, it showed a homogeneous state without phase separation.

Subsequently, the composition for comparative was prepared by mixing the main body (A-2) heated at 60 degreeC, and this hardening | curing agent (liquid temperature = 60 degreeC), The measurement of said item (1)-(8) about the composition obtained To evaluation. The results are shown in Table 7 below.

This comparative example 5 is a comparative example whose ratio of content of a short chain diol and content of a short chain triol is 50/50 (<55/45).

<Comparative Example 6-8>

In accordance with the formulation formulation shown in Table 6 below, a curing agent was prepared by mixing the components (long chain diol, short chain diol, short chain triol, catalyst) under heating at 60 ° C for 1 hour. About each of the obtained hardening | curing agents, when the state immediately after preparation (liquid temperature = 60 degreeC) was observed visually, the hardening | curing agent showed the homogeneous state without phase-separating. Each of the obtained curing agents was filled in an accommodating container, and the pores of the vessel were nitrogen-substituted and then tightly cooled to room temperature (by which each of the curing agents was solidified).

Subsequently, each of the curing agents was heated (reheated) to 60 ° C., and the state of the melted agent melted by visual observation was observed. As a result, none of the curing agents showed a homogeneous state without phase separation.

Subsequently, the composition for comparison was prepared by mixing the main body (A-2) heated at 60 degreeC, and this hardening | curing agent (liquid temperature = 60 degreeC), About each of the said composition (1)-(8) Was measured or evaluated. The results are shown in Table 7 below.

Here, Comparative Example 6 is a comparative example using DMI alone as a catalyst, Comparative Example 7 is a comparative example using octyl hydrochloric acid of DBU alone as a catalyst, and Comparative Example 8 is a comparative example using TEDA alone as a catalyst.

* 5) "PTG-2000SN": PTMG (manufactured by Hodogaya Kagaku Kogyo Co., Ltd.) with an average molecular weight of 2,000.

* 7) "2ME1, 3PD": 2-methyl-1,3-propanediol

The composition of the present invention is used for producing a paper feed roll mounted on an OA machine or the like, and the paper feed roll obtained by the composition of the present invention is excellent in productivity, and at the same time, mechanical properties, surface properties and Its stability is also excellent.

Claims (7)

A thermosetting urethane elastomer composition used to form an elastic member of a paper feed roll, The NCO content containing NCO group terminal urethane prepolymer obtained by reaction of MDI isocyanate and poly (oxytetramethylene) glycol is 5-15%, and the viscosity in 75 degreeC is 1,000 mm <2> / s or less, The main subject [A 〕Wow; (B1) long-chain diols composed of poly (oxytetramethylene) glycol, (B2) short-chain diols containing 2-methyl-1,3-propanediol in proportions exceeding 50 mass%, (B3) short-chain triol which contains trimethylolpropane as an essential component, (B4) a catalyst consisting of 1,2-dimethylimidazole, (B5) 1,5-diazabicyclo [4. 3. 0] nonene-5, 1,5-diazabicyclo [4. 3. A salt of Nonen-5, 1,8-diazabicyclo [5. 4. 0] undecene-7 and 1,8-diazabicyclo [5. 4. a curing agent [B] containing a thermosensitive catalyst comprising at least one kind of bicyclic tertiary diamine (salt) selected from salts of undecene-7; The ratio [(B1) / [(B2) + (B3)]] of the content of the long chain diol (B1) and the total content of the short chain diol (B2) and the short chain triol (B3) is 80/20 to 95/5 (Mass), The composition for paper feed roll manufacture whose ratio [(B2) / (B3)] of content of a short chain diol (B2) and content of a short chain triol (B3) is 55/45-95/5 (mass). A catalyst (B4) and a catalyst (B5) are 0.01-5 mass in total amount with respect to 100 mass parts of polyol components which become long chain diol (B1), short chain diol (B2), and short chain triol (B3). Contained in negative proportions, The composition for paper feed roll manufacture whose content ratio [(B4) / (B5)] of a catalyst (B4) and a catalyst (B5) is 100/5-100/50 (mass). The composition for producing a paper feed roll according to claim 1 or 2, further comprising a plasticizer [C]. The paper conveying roll of Claim 1 or 2 provided with the elastic member whose JIS-A hardness exceeds 60 and is 70 or less formed by hardening | curing in a shaping | molding thing which does not contain a plasticizer. The paper feed roll provided with the elastic member whose JIS-A hardness is 40-60 formed by hardening | curing the composition of Claim 3 in a shaping | molding die. A method for producing a paper feed roll, comprising the step of forming a resilient member having a JIS-A hardness of greater than 60 and less than 70, wherein the composition of claim 1 or 2 does not contain a plasticizer. . The manufacturing method of the paper feed roll containing the process of forming the elastic member whose JIS-A hardness is 40-60 formed by hardening the composition of Claim 3 in a shaping | molding die.